pH Sampling Density

A recent post by Anthony Watts highlighted a curious fact. This is that records of some two and a half million oceanic pH samples existed, but weren’t used in testimony before Congress about ocean pH. The post was accompanied by a graph which purported to show a historical variation in ocean pH.

I was unimpressed by the graph in that post, which seemed simplistic and, well, in a word, wrong. But on the other hand, I certainly found it bizarre and most interesting that someone would throw out that huge amount of scientific data. That was the reason I forwarded it to Anthony, in the hope of unraveling the actual truth of the matter.

So … as is my wont, I’ve now taken a look at the data myself, albeit at the moment a very preliminary look. The data was conveniently provided by a WUWT commenter in .csv format here, my compliments to him for the collation. He also has a good explanation of the process, along with R code. Note that there has been no quality control on the data. About 2% of the surface pH values are well outside the range of oceanic pH, and I removed them before looking further at the data.

Now, the first question I asked was, where were the samples taken? The problem with the graph in the recent post linked to above is that it lumps together samples taken in various parts of the planet. And unless the sampling is uniform in time and space, this is a Very Bad Idea™.

So I made a map that shows where each surface sample was taken. For simplicity, and because this was my first cut, I restricted myself to those samples with a depth of 0 (right at the surface), which are a bit less than a tenth of the total samples. Here are two different views of the same location data.

Figures 1a and 1b. Two views of the location of the surface samples of the global pH dataset, centered on the Pacific and the Atlantic. In some regions you can see the tracks of the oceanographic expedition vessels quite clearly.

Now, I must confess that this was a surprise to me. I hadn’t expected the concentration of samples around Japan, it appears the Japanese oceanographers mush have been quite busy. And I also hadn’t expected the high sample density in the Baltic Sea and the other enclosed seas (the Black Sea between Turkey and Russia, and the Caspian Sea to its right).

Finally, here are the average pH values by gridcell, for the entire period of record

Figure 2. Average values of pH by gridcell in the record.

Now, you can see from these maps that we cannot simply put all of that data into a single box and extract a timeline from it.

So … was there “pHraud” in not utilizing this data? I say no, there was no fraud. I say this in part because it’s so difficult to infer intent. Because I have been falsely accused of having bad intent a number of times, I’m sensitive on the subject. I dislike accusations without evidence, and I see no evidence of fraud in this case.

However, it is a huge scientific resource, two million plus pH samples taken by oceanographers over decades, and not using it without some solid scientific reason for ignoring it just doesn’t work for me. What I suspect has happened is that the mass and complexity of the data was too overwhelming, and so the investigators simply put it into the “Too Hard” pile. But that’s just speculation, the real reason may be entirely different. Regardless of the reason, I do think that the authors should have explained their omission.

In any case, that’s the story so far. It certainly appears to me that there is plenty of data there for meaningful time series extractions in some areas. There are, for example, about 400 1°x1° gridcells that have more than a hundred observations per gridcell, and groups of nearby gridcell cells combined have much more data. The North Atlantic and the oceanic area off of Japan seem like they would have more than adequate data for time series extraction.

I may or may not do any followup on this dataset, but I invite readers to use the data for their own analyses.

Regards to all,

w.

ADDENDUM: As usual, I request that if you disagree with someone, please have the courtesy to QUOTE THEIR EXACT WORDS THAT YOU DISAGREE WITH, so that we can all understand the exact nature of your objections.

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319 thoughts on “pH Sampling Density”

What about dates? The assertion is that the pH is decreasing, right? So there has to be a trend. Second, a flat average is meaningless. The data has to be kriged, and from the look of the graph, there are (as usual) huge regions that are undersampled and smaller ones that are heavily oversampled.
rgb

Yes, dates are essential. The authors didn’t say the earlier data didn’t exist. They declined to cite an annual average. That would mean they believe there wasn’t enough good data in that year, with adequate spatial coverage, to compute an average. That is what has to be checked.
GISS gives a global temperature average starting 1880. There is plenty of data from some places before 1880, but they don’t think the coverage is good enough for a global average. No one seems to think that is improper.“Note that there has been no quality control on the data. About 2% of the surface pH values are well outside the range of oceanic pH, and I removed them before looking further at the data.”
Sounds like an important caution. Sabine et al may know stuff about data quality that experts here don’t.

Nick, “No one seems to think that is improper.”
I think that is improper. I’m not “no one”.https://chiefio.wordpress.com/2011/07/01/intrinsic-extrinsic-intensive-extensive/
ANY “Global Average Temperature” is an absurd and non-physical number. Every single one.
So all you can do is FIRST and FOR ANY ONE THERMOMETER compute an anomaly trend; then average those trends and talk only about anomaly trends. (I hear 1000 keyboards preparing to say that is what is done… it isn’t.) Now realize, that means you must NOT average the Min-Max per day, and NOT average the days per month. Then NOT carry those monthly averages AS “temperatures” through the rest of your homogenizing (as GIStemp does) and only calculate a “grid cell anomaly” at the end (as GIStemp does).
Given all that machination, and all that fundamentally dumb (i.e. irrational) averaging of an intrinsic property (that can not be averaged and retain meaning as a temperature) it is highly irrational to ‘cut off’ the series at any point, or to use it with any variation in instruments in place (and expect more “averaging” to fix the induced discontinuities). It is fundamentally improper to use ANY variable set of thermometers and average them.
For a bit more depth:http://www.uoguelph.ca/~rmckitri/research/globaltemp/globaltemp.htmlhttp://www.uoguelph.ca/~rmckitri/research/globaltemp/GlobTemp.JNET.pdf

ABSTRACT:
Physical, mathematical and observational grounds are employed to show that there is no physically meaningful global temperature for the Earth in the context of the issue of global warming. While it is always possible to construct statistics for any given set of local temperature data, an infinite range of such statistics is mathematically permissible if physical principles provide no explicit basis for choosing among them. Distinct and equally valid statistical rules can and do show opposite trends when applied to the results of computations from physical models and real data in the atmosphere. A given temperature field can be interpreted as both “warming” and “cooling” simultaneously, making the concept of warming in the context of the issue of global warming physically ill-posed.

Ross is not “no one” either…Per pH variation
It is also essential that Time Of Day and level of sunshine is known. Daily pH cycling in surface ocean levels can be fairly large based on relative photosynthesis / respiration of the stuff living in it… So if you do not know the TOD profile and the insolation levels, you might be only indirectly measuring sunshine and fertilizer…

What about dates? The assertion is that the pH is decreasing, right? So there has to be a trend. Second, a flat average is meaningless. The data has to be kriged, and from the look of the graph, there are (as usual) huge regions that are undersampled and smaller ones that are heavily oversampled.

Nick Stokes December 30, 2014 at 4:13 pm Edit

Yes, dates are essential. The authors didn’t say the earlier data didn’t exist. They declined to cite an annual average. That would mean they believe there wasn’t enough good data in that year, with adequate spatial coverage, to compute an average. That is what has to be checked.

Dang, guys, take a deep breath. You might want to re-read what I said at the onset:

So … as is my wont, I’ve now taken a look at the data myself, albeit at the moment a very preliminary look.

So yes, the dates are important. And yes, a more detailed quality control is important … but it’s a PRELIMINARY LOOK.
Next, a flat average is not “meaningless”, as it allows us to see what the average pH is (according to their measurements) in various areas of the ocean.
Finally, if you want a better analysis, re-read what I said above:

I may or may not do any followup on this dataset, but I invite readers to use the data for their own analyses.

I’m just moving the project down the road. I made no claim as to its completeness, just increasing our understanding.
w.

Well, I’ve downloaded the data. I allowed down to 1 m depth (not just 0) and got 202354 points (min pH 0). I did a table over years. No QC.
I don’t think this was Sabine’s data. There is very little after about 1990; it’s mostly between then and 1960. Best year was 1978 with 7106 total.
Now even if that was uniformly distributed, it would be far too little. People here complain about the reduced size of GHCN. That has about 1800 stations with about 12 readings per year. And they are reasonably well distributed. Here we have at least double the area, and at best about 1/3 the points, with obviously eccentric distribution. And then with QC…

Lance W,“Strangely enough, this is the exact period (1989-2007) chosen by Feely to illustrate the drop in pH:”
Yes, but the dataset is the one chosen by Mike Wallace, with all the “omitted data”. It’s unlikely to be what Feely was using for the post-1988 period.

” People here complain about the reduced size of GHCN. That has about 1800 stations with about 12 readings per year. And they are reasonably well distributed. ”
Ahaha! Really, how many of them are in the middle of oceans?

Nick Stokes:
I write because it is rare for me to agree with you so I welcome this opportunity to do it.
You say

Well, I’ve downloaded the data. I allowed down to 1 m depth (not just 0) and got 202354 points (min pH 0). I did a table over years. No QC.
I don’t think this was Sabine’s data. There is very little after about 1990; it’s mostly between then and 1960. Best year was 1978 with 7106 total.Now even if that was uniformly distributed, it would be far too little.

Emphasis added by me: RSC
I very strongly agree and I have repeatedly made the same point about this data – including making it on WUWT – whenever Ferdinand Engelbeen has cited this data.
The data is far too sparse in spatial distribution and over time for it to be meaningful as indicator of the putative alteration of average oceanic pH resulting from increase to atmospheric CO2 concentration over the last century.
Richard

Lance, the graph of the other Wallace is solely based on glass electrode pH measurements, which are near completely abandoned in recent years as too unreliable (with a lot of care not better than 0.1 pH unit) to measure a general pH drop of theoretically 0.1unit since 1850 (with about 50% of the CO2 increase since 1984 in the atmosphere) since the start of the industrial revolution. Moreover his pH drop of 0.3 pH unit since 1984 is not the result of a global or local pH drop, it is the result of the random sampling in different places and different seasons.
The curves by Sabine, Feely, Bates and many others are based on either calculated pH, or pH measurements based on far more accurate colorimetric pH measurements or both. They excluded glass electrode pH measurements as too unreliable.
pH can be calculated by (over 80 years) established ocean carbon chemistry from other, better defined measurements like TA (total alkalinity) and DIC (dissolved inorganic carbon).
See: http://www.pnas.org/content/106/30/12235.full.pdf
for a description of the methods and the trends at Hawaii, where both methods were used.
Before 1992 direct pH measurements were by glass electrode:http://hahana.soest.hawaii.edu/hot/methods/ph.html
but not used in their graphs
For Bermuda:http://www.biogeosciences.net/9/2509/2012/bg-9-2509-2012.pdf
computation of pH is mentioned in chapter 2.7
More data for several fixed stations can be found at:http://www.tos.org/oceanography/archive/27-1_bates.pdf
Then the data for regular sea cruises by research ships, here for Japan:http://www.data.jma.go.jp/kaiyou/english/oa/oceanacidification_en.html
And there is an interesting PH.D. work about the results from cruises in the Southern Oceans which tries to combine pH measurements with calculated pH over time (-0.03 +/- 0.03 pH unit since 1972):http://scholar.colorado.edu/cgi/viewcontent.cgi?article=1456&context=honr_theses
which contains many interesting points and graphs. Especially the graphs of the distribution in time and latitude of the measured and calculated values (page 46) is interesting.
More to learn about carbonate chemistry in the oceans in a nice overview:http://www.soest.hawaii.edu/oceanography/courses/OCN623/Spring2012/CO2pH.pdf

Richard,
The compilation by Wallace is unreliable, because he didn’t sort on place and seasons. Regular cruises over the same tracks give a better insight, even if done with less accurate equipment. It is better to recalculate pH from other, more frequently measured variables like TA and DIC, but that is a hell of a job to sort out.
Anyway, you don’t need to monitor all parts of all oceans frequently each year, as ocean chemistry is the same everywhere and the changes caused by (seasonal) temperature (and accompanied bio-life) changes level off after a full seasonal cycle. Ocean pH is directly influenced by atmospheric CO2 levels, which influence at any place of the oceans can be calculated if a few local variables are known. It would be quite strange if none-monitored open ocean places would show an increase of pH with increased CO2 in the atmosphere (far more variable at upwelling places and estuaries).
All fixed stations and repeated cruises show a declining trend since 1984. All in ratio to increasing CO2 levels in the atmosphere.
A compilation of Southern Ocean cruises (31,700 measured + 41,800 calculated pH values) also shows a declining trend since 1972.
(links are currently under moderation, will be shown soon).

Anyway, you don’t need to monitor all parts of all oceans frequently each year, as ocean chemistry is the same everywhere and the changes caused by (seasonal) temperature (and accompanied bio-life) changes level off after a full seasonal cycle.

I find this difficult to believe, Ferdinand. I know the salinity of the ocean varies quite a bit from location to location. And although salinity does not directly affect pH, I can believe the chemistry of the ocean that does affect pH also varies quite a bit by location.

What appears to be fraudulent about the Feely/Sabine study is that they apparently failed to mention that they had used mostly modeled data and that only the data since 1988 were measured. Had they been a bit more forthcoming in their study, they would have mentioned the existence of the full set of measurements and provided their rationale for excluding it. They also would have explained how they got the data they did provide in their time series plot. With the history of the IPCC climate models, there is good reason to have serious doubts about any modeled data.

Lance, the data from NOAA were further gridded Berényi Péter in 5×5 deg boxes and found near zero trend over the past 30 years for all gridded boxes. The error margin still is large +/- 0.03 unit per decade for the glass electrode measurements, where the modern measured/calculated methods show a trend of around -0.015 unit per decade, largely within the error margins of the glass electrode measurements.
What we already can conclude is that the glass electrode pH measurements can’t show the trend over the past 30 years and that the compilation of the other Wallace doesn’t show a real pH trend, but the result of random sampling in place and time.
Indeed it should be possible to use the other historical measurements to calculate the pH of that moment. The last reference I sent was for a PhD work which has done that for all known data for the Southern Ocean. Seems a lot of work, but maybe programmable now that all data are in computer readable form…

Ferdinand…their fig 4 pH from your Hawaii link….just looks like a sine wave…no steady decrease in pH at all
honestly, it looks like if they had started in 1979 and stopped in 2007, they would have shown a huge increase in pH
Looks like a temp graph where you cherry pick your time to show anything…and frankly, seeing it that way makes it clear that any wiggles in pH, either up or down, is just nothing more than that…..a wigglehttp://www.pnas.org/content/106/30/12235.full.pdf

Doesn’t krigging assume a smooth spread? Is there any reason to believe the ocean pH is properly represented by a smoothed even spread? a lack of “hot” or “cold” spots? spots of upwelling acidic or basic water from underwater features or events? should these be kirgged away? or krigged over?
Does the ocean even have “an average pH” that could be going up or down? or is this just another invented concept created for propaganda purposes — world in danger or world resilient? is it just another weapon in the Climate Wars?

Does the ocean even have “an average pH” that could be going up or down? or is this just another invented concept created for propaganda purposes — world in danger or world resilient? is it just another weapon in the Climate Wars?

I provide my answers to each of your three questions in turn.
Q1
Does the ocean even have “an average pH” that could be going up or down?
A1
Possibly, but probably not
(see comment by Lance Wallace at December 31, 2014 at 3:53 pm).
Q2
is this (i.e. “an average pH”) just another invented concept created for propaganda purposes — world in danger or world resilient?
A2
Yes.
Q3
is it (i.e. “an average pH”) just another weapon in the Climate Wars?
A3
Yes.
Richard

The gridded result:Berényi Péter December 31, 2014 at 8:58 am
A preliminary look at the data shows beyond doubt, that ocean pH is decreasing indeed, at a rate of -0.002±0.038/decade. In other words, it is absolutely stable.
delivers virtually the exact same answer as simply treating the data as a random sample, without any gridding, averaging, anomalies, adjustments, etc.ferdberple December 31, 2014 at 8:29 am http://oi60.tinypic.com/9s7xvo.jpg

I agree, Norm. Actual pH will vary considerably due to temperature, salinity, calcium carbonate content, etc., which makes some previous comments about the chemistry of the ocean being the “same everywhere” suspect, IMHO.
One point I have not seen yet is the impact of the temperature compensation of electrode pH meters. Many meters have both electrode temperature and actual temperature compensations that are often set to correct the reading to 25C. I have no idea of what type of data we are getting. However, I know I would like to see the actual pHs, because that is what the sea life is encountering.
Last point about “average pH.” You might think the average of pHs 7.0 and 8.0 is 7.5. But due to the logarithmic nature of pH, the average is actually 7.26. So unless your averaging program first converts the pHs to actual H+ ion concentrations, then averages them and takes the log of the results, then you will not have accurate averaging.

Can the data be resolved into decadal trends? In addition to “where”, “when” the sampling was conducted is crucial. The lower pH around the Bering Sea and northeastern Pacific could easily be dominated by upwelling events that are modulated by the PDO. Average pH could be skewed by the time of sampling.

Willis
The methods for taking co2 samples since 1820 And up to the time that keeling started Sampling at mauna loa have been roundly criticised. Is the method for taking these ph samples considered robust and consistent bearing in mind the number, the time scale and the variety of people taking them?
Tonyb

good grief! The gremlins ate much of my comment above.
To paraphrase, bearing in mind the complaints about historic co2 readings that were regularly taken from 1820 up till Keeling changed the methodology in the 1950’s, can we be certain that these historic ph readings are robust?
tonyb

Hi Tony, ferdberple does show a plot of all sampled pH data over the years near the end of the discussion. Has a similar look as the cloud of CO2 data from the many samples taken in the past… pH data ranging from zero to 14???
I agree with Sabine: most of the data are not reliable but may give some idea if sorted for place and season…

oh, I think I see what it was….
The Japanese use “scientific research” as an excuse for whaling, tuna, fisheries…
…so their commercial fishing fleet takes measurements every time they go out
That’s why the sample density is so high there..
Better??

“It occurs to me that adding additional CO2 would result in the precipitation of CaCO3 as it exceeds it’s solubility, rather than it would lower the pH.”
You need to work with the solubility product here. Solubility .001M doesn’t help, because it assumes no excess ions present. The solubility product is that of Ca++ and CO3–. The reason added CO2 dissolves CaCO3 is that, which it adds carbon, it converts CO3– to HCO3-, thus reducing the product.

Carbon dioxide in solution forms a buffer solution with the form taken the carbon dioxide strongly dependent on pH:
CO2 + H2O H2CO3 (carbonic acid) upon becoming absorbed by water
At low pH it forms bicarbonate ion
H2CO3 H+ + HCO3- (balance point pH 6.37)
At intermediate pH bicarbonate forms carbonate
HCO3- H+ + CO3(-2) (balance point pH 10.36)
At higher pH it is predominantly present as carbonate.
At the prevailing pH of most sea water, about 8.3 to 8.4, the CO2 present in sea water is almost entirely present as bicarbonate, with barely 1% of it present as carbonic acid and another 1% present as carbonate ion.
This is good because the bicarbonate form is the only form biologically available for foraminifera, coral, mulloscs and other sea life that forms calcium carbonate structures.
CaCO3 ‘precipitated’ by sea water (eventually forming limestone, chalk, marble, etc.) was formed by living cells.

I think you are right, the enormous amount of data accumulated over a long period will take a lot of time to analyse and quite possibly will not come to the conclusion that the analysts would prefer.
On the other hand, there would be a PhD for someone with the integrity to do an honest breakdown and dissection of the data – assuming that they could find an academic establishment to review the result dispassionately.

There was a PhD work done on part of the data for the Southern Ocean (2012), partly on measured, partly on calculated data:http://scholar.colorado.edu/cgi/viewcontent.cgi?article=1456&context=honr_theses
I suppose that he used all available data for the Southern Ocean, as that was very sparsely sampled in the past…
The result, with large margins of error: -0.3 +/- 0.3 pH unit over the period 1972-2011

This was a ‘senior thesis’ paper in receiving an undergraduate BS degree, and not a PhD. First couple of lines is all one needs to read to understand the direction of paper. Granted, most ‘senior thesis’ never come anywhere close to this attempt, but one also only needs to look at the principal ‘contributor’ as well (likely thesis adviser).

Another issue is how long were sample maintained before pH was determined. Samples were often taken during cruises and then analyzed weeks to months later. There was no systematic timeline for nalaysis. Bottles locked away in the dark prevent photosynthesis that could increase pH, but cellular respiration from bacteria would continue and could create a drop in pH.

One should see wider seasonal and decadal variations with seas like the Black Sea that are more ‘landlocked’ than the open oceans. Most of the Black Sea’s bottom waters are devoid of oxygen. I would think that similar such situations be graphed separately, rather than dumping all data into one graph. Also, rates of inflow and outflow would have to be accounted for.

In a local lake in the Gatineau Park, Canada, there is a lake which is a left-over from the last ice-age. It’s called Pink Lake, and the Oxygenated water only goes to 60 feet, below the oxy-xline, ithe water is oxygen free. Scuba diving i9s forbidden there.http://www.ncc-ccn.gc.ca/places-to-visit/gatineau-park/pink-lake

New dams that have a lot of vegetation in the flooded area also have a poor distribution of oxygen. Below the oxy line there is a high concentration of H2S. If deep water is released from such a dam into the river below, it kills everything in it. Thus it is common to release some of the deep water and mostly top water while monitoring the mix downstream. It is easy to get it wrong.
Good dam management has to address this issue constantly. I suspect there must be a lot of lakes like Pink Lake in other parts of Canada. Being deep helps create such an unwanted boundary.

What I suspect has happened is that the mass and complexity of the data was too overwhelming, and so the investigators simply put it into the “Too Hard” pile.
I aplolgise for not accepting this idea. You have managed to make something of it in a short timescale and I have no doubt that you or someone like you would be able to do much more if time was available. Time was available to the original ocean acidificationists and they chose not to do it. That tells me a lot.

What I suspect has happened is that the mass and complexity of the data was too overwhelming, and so the investigators simply put it into the “Too Hard” pile.

I aplolgise for not accepting this idea. You have managed to make something of it in a short timescale and I have no doubt that you or someone like you would be able to do much more if time was available. Time was available to the original ocean acidificationists and they chose not to do it. That tells me a lot.

Mmmm … you may be correct. Although I’d add that I work a lot with big datasets, and I’ve developed my own tools to do the mapping and analysis in a short time. So the idea of crunching two and a half million individual records doesn’t faze me, but others might not be so sanguine about the project.
As I said, we don’t know at this point why the data weren’t used. And until we have a clear answer to that question, allegations of fraud are out of line.
w.

Willis says ” We don’t know at this point why the data weren’t used”
I thought we did. Sabine and Englebeen have said words to the effect that the data did not provide the “signal” that was sought, the signal being the decrease in oceanic pH. They wanted that “signal” and they had to fabricate the data to provide it. This was done by hind casting a trend of declining pH via modeling.

You would think that any reasonably competent researcher setting out to look at global oceanic pH would be prepared to deal with large data sets over large areas. If not, how could they expect to produce valid results?

mpainter, thanks for the alleged motives…
There are two problems with the data:
– the accuracy of the glass electrode pH measurements: 0.1 pH unit, while the theoretical trend from 1850 to 1984 was about 0.05 pH unit.
– the lack of data for the same parts of the oceans in the same seasons over a longer period.
The theoretical trend is confirmed since 1984 at seven fixed station at different places over the oceans, based on more accurate direct (colorimetric) pH measurements and calculated pH (which overlap each other).
The theoretical trend is confirmed since 1972 for the Southern Ocean based on direct (glass electrode) and calculated measurements (31,700 measured + 41,800 calculated pH values), be it with large margins of error: -0.03 +/- 0.03 pH units:http://scholar.colorado.edu/cgi/viewcontent.cgi?article=1456&context=honr_theses
Here the distribution over time of the measurements:http://www.ferdinand-engelbeen.be/klimaat/klim_img/ph_sh.jpg
no direct measurements in the period before 1990…
If you see any reason that the pH of the open oceans in general wouldn’t show a faint drop with increasing CO2 in the atmosphere in the period before 1984, I am very interested to hear it…

Ferdinand :
The whole problem with climate science is that theory is substituted for facts and facts are invented. If you cannot see the fault of Sabine and Feely’s methods, then perhaps you share those faults. Do approve of the method of presenting model product as observed measurements, giving no hints of how the data was actually derived?

mpainter, I don’t see much problems by presenting modeled data for the period before 1984, because in this case the modeled data are much better than the measured data, which are widely around the model (contrary to climate models), where the (chemical) model is confirmed in the period after 1984.
The only point is that Feely/Sabine should have made it clear that the early part and the “future” part of the graph was from a model, because the observations were not accurate enough.

Hi Willis, I appreciate you are trying to see both sides of the issue, but I find it difficult to imagine a legitimate reason for discarding, not even mentioning the data, and replacing it with a computational model which is based on – what?
I mean, try to imagine this in the context of a high school chemistry class. “Sorry teach, the practical experiment I did produced some difficult to analyse values, so I threw out the data and based my conclusion on a mathematical model of what I think should have happened … yes, I know I didn’t mention the data I discarded, but you see the data was no good… ” – that conversation would have rapidly concluded in an “F” for that assignment.
It might be that different rules apply when you producing reports which influence the expenditure of billions of dollars of taxpayer money, but I can’t help viewing such “lapses” from the perspective of what it would have meant to me, back when I was being taught about science.

Has anyone attempted to calculate just how much carbon dioxide would be required to change the pH of the oceans to any significant extent? It seems to me that given the density of sea water and the volume of that water, compared against the equivalent values for atmospheric CO2 and the fact that CO2 in aqueous solution is a weak acid, never mind the ample buffering in the oceans, the numbers calculated for carbon dioxide requirements would be very large indeed.

Indeed. I did a simple calculation during the BP oil spill in the Gulf of Mexico. It was a tragedy, no question, but the amount of oil spilled there was on the order of one drop per billion (sorry, don’t have the numbers anymore). The oceans are massive, it takes massive amounts to ‘Fundamentaly” change them.

Because the increase of total carbon (DIC, CO2 + bi + carbonate) in the ocean surface is measured…
If the pH drop was caused by e.g. undersea or land volcanoes (SO2, HCl, HF,…) the pH would drop and expel CO2 (reducing DIC). If the pH drop is caused by more CO2 in the atmosphere, DIC increases…

That calculation is made and quite easy to do: one can even calculate the pH from the oceans during an ice age (8.367). All you need is the amount of CO2 in the atmosphere: that is in fast equilibrium with the CO2/bi/carbonate system in the ocean surface and the rest is established ocean carbon chemistry of already 80 years ago:http://biocycle.atmos.colostate.edu/shiny/carbonate/

Sorry, forgot to add: the increase of 110 ppmv (30%) in the atmosphere gives an increase of DIC of about 3% in total carbon (DIC) in the “mixed” layer of the oceans (0-200 m depth), depending of the Revelle/buffer factor. That gives a change of about -0.1 pH unit since 1850. The exchange with the ocean surface layer is very fast (1-3 years), with the deep oceans much slower.

That calculation is made and quite easy to do: one can even calculate the pH from the oceans during an ice age (8.367). All you need is the amount of CO2 in the atmosphere: that is in fast equilibrium with the CO2/bi/carbonate system in the ocean surface and the rest is established ocean carbon chemistry of already 80 years ago:http://biocycle.atmos.colostate.edu/shiny/carbonate/

Well, yes, the calculation is “quite easy to do” and it does give an answer, but the answer is probably wrong (both for the present situation and for “during an ice age”).“That calculation” assumes that only inorganic chemistry is affecting ocean pH but – in reality – it is observed that biota affect ocean pH, too.
Richard

Richard, the data of Willis show a higher increase of DIC than I reported as the real ratio depends of the “Revelle” (buffer) factor and temperature which changes with latitude. Anyway, the 30% change of CO2 in the atmosphere gives the same change as free CO2, but a much smaller change in total CO2 (DIC) and a very small change in pH.
That can be seen for the different stations:http://www.tos.org/oceanography/archive/27-1_bates.pdf
Fig. 3 and Table 2.

I assume the data have been averaged to produce the earlier graph? Given that pH is a negative log of a concentration, how is the averaging carried out?
How meaningful is any such average, especially in a buffered solution such as sea water?

The analysis was done here:http://www.co2web.info/ESEF3VO2.htm
Acidification is not really possible in a buffered solution like the ocean. Yes you will get local highs and lows but they will not last. The only way you can get a buffered solution to change pH permanently is to use up all the buffering agent. I know since I used to analyze Deionized river water where the organic content buffering the water changed on a daily basis.
Also consider basalt as a buffering agent as well as limestone.
Seems since all the rest of the ‘evidence’ has proven to be junk they are trying to recycle the tired old ‘Ocean Acidification’ again. I though that beast had already been slayed.

Gail, this is not a conventional buffer system which you’d find in the lab. In a normal buffered solution the pH is close to the pKa value for the buffer, being a diprotic acid carbonic acid has two pKa’s, 6.3 and 10.3, the ocean is nowhere near these! Addition of CO2 changes the equilibrium system of the ocean towards lower pH.

“The only way you can get a buffered solution to change pH permanently is to use up all the buffering agent.”
That isn’t true at all. Every time you add acid or base, you shift the pH. The rate of change is reduced by the buffer, but not to zero. The formula is Henderson–Hasselbalch:
pH=log(pKa)+log([A-]/[HA])
for acid HA.
The graph of this is called a Bjerrum plot. You can calculate the seawater pH changes here.

Nick, that again assumes all buffering is chemical. Biological activity is not included, and likely changes the result. In addition, if surface winds change over time, the mixing depth changes, and affects the surface average.

Adding acid to a buffer will lower the pH and adding base will raise the pH, but the changes will be less than without buffer. That is basic introductory chemistry. With a well designed buffer (equal amounts of acid and conjugate base and a reasonably high concentration of both) the pH changes can be very small. But the ocean is not such a buffer. The bicarbonate concentration is a little under 2 mmol/kg and the carbonate concentration is a tenth of that. The sort of buffer that one would use in the lab would have at least 10 times the bicarbonate and 100 times the carbonate. So although seawater is buffered, it is very poorly buffered.
Carbonate sediments add greatly to the buffering capacity of the ocean, which is why high CO2 levels in the distant past did not produce acidic oceans. But that is only effective on very long time scales – at least thousands of years, if not much longer. So that will be of no use in buffering the ocean against a big CO2 increase on a time scale of a century.

Mike M
I didn’t seen you make any mention in your analysis of living organisms in the ocean – just the chemistry. As the organisms have a powerful influence on time scales of weeks, not 1000 years, I suspect the buffering is much larger than you infer.
There are many areas of the ocean that are short of one or two minerals so biota are limited by that. Iron is a common deficit. There are several ‘buffers’ that are not able to function now because of a lack of CO2. There is a paper on buffers including one that is still non-functional (several papers actually) focusing on the main ‘El Nino area’ off the coast of South America. The ocean does not act like a beaker of solution. It is filled with life that needs and sequesters CO2.
Personally I doubt the ocean, under any conceivable scenario, could be neutralized. As one commenter said a few days ago, the oceans will not become acidic until the planet runs out of rocks.

Gail, Segalstad and Jaworowski as reference is a weak shot, to say the least…
Seawater is a weak buffer, not a strong one. A 30% increase of CO2 in the atmosphere over 160 years gives a 3% increase of carbon (DIC) in the ocean surface and that gives a pH drop of 0.1 unit.
Hardly measurable with the old equipment, accurate to 0.1 pH unit and zero influence on fish and other creatures in the oceans. The pH drop is mostly near the surface, as the exchange with the deep oceans is very slow. But is measured since 1984 (-0.04 pH unit) with more accurate equipment and calculated from other variables…

Ferdinand, you continually refer to the poor accuracy of old pH equipment, which is only accurate to o.1 pH unit, and is trying to detect 0.1 pH change. Yet the claims of global warming are based mainly on thermometers that are accurate or read out with resolution of 1 degree C or more, and at locations that are several degrees C different from nearby locations. The total global change is less than 0.8 C over the last 150 years. Do you believe the thermometer data set, but not the pH meter set, and why?

Leonard, I have the same doubts of the thermometer trends as of the pH trends, only the pH trends are even worse as that aren’t even fixed places…
I suppose that the satellite measurements are a lot more reliable as these scan most of the surface and don’t have problems like UHI effects. The same for the more recent pH measurements as these are at fixed places and better equipment…

Willis,
Thanks for that! As you have spent a far amount of time off-shore I accept that explanation, that now makes sense. I like that from your estimation they would be indicative of oceanographic ships. There is an obvious intention there.

thus the definition of supersaturated…..
As you add an acid…more buffer comes into solution
Like Gail said…you can’t lower pH until you deplete the buffer…..and that would mean dissolving the entire sea floor..and ignoring the fact that CO2 + plankton/cyano = buffer

CO2 exchanges are mostly in the upper 200 m of the oceans, as that is where most of the fast exchanges with the atmosphere is. Most carbonate rock is deeper and takes more time to dissolve… the pH change of ~0.04 unit is measured at a lot of places sine 1984…

Corals evolved in the Cambrian Era with atmospheric CO2 20X higher than at present. The oceans are buffered by alkali rock.
Thus Gail’s point about basalt. Though you can’t discard the mantling of the sea floor by both biological and mineral accumulations which would likely run either considerably more neutral or even slightly acidic.

Dave
Most geoscience projects have these problems. In the oil and mining industries data is commonly sparsely and irregularly sampled (both in time and space). Statistical methodologies have been developed to deal with these exact issues. Even with regular and well sampled observations the issues similar issues still exist.

The devil is in the details. What assumptions accompany the statistical adjustments, what lines of linear interpolation, what allowances for biological processes, tempurature and ocean circulation?
These can be varied a substantial amount and still meet the objectives of the scientists doing the work. It’s not good data, not good enough to justify the alarm bells.

Dave says…” It’s not good data, not good enough to justify the alarm bells.”
=============================================================
Indeed! Not only is the measured result, even given the best methods, inadequate, but just like in CAGW, the “C” is simply MIA. There are many studies documented at CO2 science which well demonstrate BENEFITS of CO2 in the oceans, and others that show that the theorized harms will not happen!
I note that Ferdinand is consistent in NOT advocating any claimed disastrous harms from the very minor PH changes. I also note the quality of responses to him, and consider this to be a very good example of scientists doing real science, a form of online public peer review.
One of the points Ferdinand makes is that the entire ocean is only in play over long time periods. I would like to suggest that the greater the potential change in the upper 200 meters manifests, the stronger the buffering influence of lower depts. of oceans would occur. n other words, I do not think the buffering affect of the lower depths is linear, just as the greater the increase of surface T manifests, the more lower upwelling o un-warmed water would counter the T increase.
Also, in addition to the many legitimate concerns with any and all attempts (even using the best equipment) to measure the global oceans PH flux, a think not only the date of measurements is critical, but the time of day is critical, as local PH flux daily in many areas is large. Also perhaps poorly considered is decadal changes in ocean currents and disparate ENSO conditions. Those two factors, in conjunction with the massive size of the oceans surface and their DEPTHS, widens the error bars to all the different attempts to measure ocean PH changes.
At any rate, to not even mention the two plus million prior readings, and to intermix modeled results with actual data without clearly noting the difference to political decision makers, is in my view not excusable.

And unless the sampling is uniform in time and space, this is a Very Bad Idea

Why? You can only work with what you’ve got. In most areas of engineering and science this is exactly the situation you have to deal with.

you can see from these maps that we cannot simply put all of that data into a single box and extract a timeline from it

Why not you could simply grid them using kriging for each year to achieve a global estimate (alternatively simple declustering method using Veronoi-type methods). Then from each yearly estimate you can construct a time series. Kriging has added bonus of supplying kriging variances as proxy to confidence.
Both suggested methods implicitly deal with data clustering. Of course there are nuances that may need to be addressed (such as choice of kriging method, whether to work in polar or Cartesian domains etc.) but these are always considerations. The temporal issue is not such an issue if you’re modelling a global summary statistic as long as the experimental approach is constant.
[Fixed italics/blockquotes. .mod]

OK, an engineer’s question about the scale of all this. Atmospheric mass is ~5.15×10^18 kg. The mass of all of the CO2 currently in our atmosphere is around 2.0×10^15 kg. Mass of the oceans is somewhere around 1.4×10^21 kg. If we dissolve every single bit of atmospheric CO2 into the oceans that’s a change of a little over 1.4 ppm. Chemists, how acidic would 1.4 milligrams dissolved CO2 make one liter of sea water? (or 1 mole of CO2 in 32,428 liters of water.)
Am I missing something here besides the buffering?

If you consider the fact that greenhouse operators add CO2 to the interior atmosphere now, then it is highly likely that plants are already suffering. When you consider the amount of primary productivity that dinosaurs required, and that the planet currently could not support a population dinosaurs comparable to the Jurassic or Cretaceous, it seems pretty certain. My favorite speculation is that the similarity between the present and the late Permian might mean the same termination. Since the end of the Permian was cold (like now in fact) and CO2 was very low (not quite as low as the present), there seems to a reasonable possibility that inadequate primary production ended the Paleozoic and ushered in the Mesozoic. So, we are experiencing a “wave of extinctions” they say. What comes after Cenozoic, and is human CO2 output slowing the onset?

Duster, If I remember correctly the O2 levels rose throughout the Mesozoic as well. All that evil plant life gorging itself on that excess planet killing CO2. Dinosaur’s size increased along that same time line. Simple correlations but does certainly suggest that CO2 is good for life and not bad. Wonder why the Climateers can’t get their heads around that concept?

“Chemists, how acidic would 1.4 milligrams dissolved CO2 make one liter of sea water? (or 1 mole of CO2 in 32,428 liters of water.)”
That amounts to an increase in dissolved inorganic carbon (DIC) of about 0.031 mmol/kg, which would lower the pH by about 0.06 pH units.
What you are missing is that the oceans mix very slowly, so the emitted CO2 that has dissolved in the ocean is mostly in a very small fraction of the ocean volume. The estimated change in mixed layer DIC since pre-industrial times is 0.056 mmol/kg, producing a calculated pH change of 0.11 pH unit. Double CO2 would increase DIC by a further 0.064 mmol/kg and triple CO2 would add 0.054 mmol/kg beyond that. The corresponding pH increments are 0.14 and 0.15 pH unit. With triple CO2, carbonate in the mixed layer would be just over half its pre-industrial concentration.
At some point, cranking up CO2 will be a problem. Personally, I am skeptical about that happening soon.
My source for the numbers is:
Kleypas, J.A., R.A. Feely, V.J. Fabry, C. Langdon, C.L. Sabine, and L.L. Robbins, 2006. Impacts of Ocean Acid- ification on Coral Reefs and Other Marine Calcifiers: A Guide for Future Research, report of a workshop held 18–20 April 2005, St. Petersburg, FL, sponsored by NSF, NOAA, and the U.S. Geological Survey, 88 pp.
Although I downloaded it from the web some years ago, I no longer have the link.

OK, so starting with a clean “back of the envelope” and looking at the whole of man’s contribution to CO2 instantly dissolved in the mixed layer the numbers are close to the same. Consider mixed layer average of 150m (throwing out the < 50m warm shallows and the 1000m deep near freezing polar zones) that’s 5.415×10^19 kg for water mass. Man’s contribution to atmospheric CO2 is 9.05×10^13 kg (with proper mass fraction values, my previous math was based on volume fraction… oops.) That’s still only 1.67 mg/kg CO2 in sea water or 0.038 mmol/kg. (I also used 1kg/l so I’m ignoring everything else in sea water mass wise.)
That still doesn’t make for a pH change that gets outside the real working differences of current pH meters and standard calibration solutions. And I’m assuming all the CO2 goes in at once and is 100% mixed. I’m not real worried about this.

I would like to suggest that the greater the potential change in the PH of the upper 200 meters manifests, the stronger the buffering influence of lower depths. of oceans would occur. In other words, I do not think the buffering affect of the lower depths is linear, just as the greater the increase of surface T manifests, the more lower upwelling of un-warmed water would counter the T increase

Not a matter of quantities, a matter of pressure differences and equilibria:
– a 30% CO2 increase in the atmosphere for a certain water temperature gives a 30% increase of free CO2 (gas) in the oceans surface (Henry’s law).
– a 30% increase of free CO2 in the ocean surface gives a 3% increase in total carbon (DIC) in the ocean’s surface (chemical equilibria).
– a 3% increase in DIC gives a pH drop of 0.1 unit in the ocean surface.
Change is mostly in the surface (0-200 m) as the deeper oceans show much less exchange…

Very nice, but one question; with a ~30% supposed increase in CO2 in-atmosphere yielding a ~3% increase in DIC, what is the calculated increase in Biomass? Oh, you don’t have that? So much for organic equilibrium.

CO2 was as high as 7,069 ppm 520 Mya and 12,000 ppm at 635 Mya.
That is 253% and 428% higher than the pre-industrial equilibrium.
So your math Ferdinand, provides for ocean pH’s of 5.4 and 3.4 respectively for the periods just when complex life was evolving.
On the other hand, many life-forms have pH’s in that range.
I think we need a new formula. Those numbers do not sound right.

James,
The 30% increase of CO2 in the atmosphere has some influence: the earth is greening with 1 GtC/year or 10% of the human emissions, as CO2 is one of the limiting factors for land plant growth.
The 3% increase in DIC in the ocean surface has hardly any influence on bio-life in the oceans as CO2 (as bicarbonate) is not the limiting factor for algae growth. The summer/winter difference at Bermuda is not more than 2,5% of DIC. Trace elements like iron are the main limiting factors…

Bill Illis, you forget that Ca and Mg were also far more abundant in the oceans… Meanwhile lots of the combination can be found as carbonates in the white cliffs of Dover (UK), the Dolomites (Italy), the karst landscapes of Ireland, the caves of Carlsbad (USA) and many other places…
But there are several web sites where you can calculate the (theoretical) pH and other ocean related data for any more recent period on earth, including ice ages:http://biocycle.atmos.colostate.edu/shiny/carbonate/

Not a matter of quantities, a matter of pressure differences and equilibria:
– a 30% CO2 increase in the atmosphere for a certain water temperature gives a 30% increase of free CO2 (gas) in the oceans surface (Henry’s law).
– a 30% increase of free CO2 in the ocean surface gives a 3% increase in total carbon (DIC) in the ocean’s surface (chemical equilibria).
– a 3% increase in DIC gives a pH drop of 0.1 unit in the ocean surface.

Thanks, Ferdinand. While you are correct as far as that goes, it’s somewhat more complex than that, as you’ve assumed that both total alkalinity and salinity are constant … which is generally not true.
w.

Ferdinand, as a real-world example, consider the Hawaii HOT time series of surface measurements of seawater from 1988 to 2012. During that time, CO2 rose by 12.1%. From your rules above, we’d expect a change in DIC of 1.2% … but in fact over the same period the DIC rose almost twice that amount, 2.2%.
Regards,
w.

Willis,
For the ocean as a whole, alkalinity and salinity are essentially constant on a time scale of centuries. There may well be small local variations. I plan to have some fun looking at the data you provided.
Bill Illis,
On geological time scales, alkalinity (and perhaps also salinity) will not be constant. Alkalinity is the total capacity of a solution to neutralize acid. For the oceans, that means that
alkalinity = [HCO3-] + 2*[CO3=] + minor bases (such as borate and phosphate)
A more acidic ocean will cause sediments, especially CaCO3, to dissolve. More CO2 in the air means more acidic rain which would increase the weathering of rocks. On geological times scales, that will raise the alkalinity and counteract the effect of higher CO2 partial pressure on the pH of the ocean.
Past episodes of high CO2 occurred slowly compared to what we are doing. I would not be surprised if raising CO2 30 times in a million years would have less effect on ocean pH than raising CO2 by a factor of 3 in 100 years.

Willis,
You will notice that in the data set there is a column labelled DIC and another labelled nDIC. The latter has some sort of salinity correction. The P_CO2 values in the file change by 13% and the nDIC changes by 1.3%, right in line with Ferdinand’s numbers.
Salinity and alkalinity have a slight upward trends, I don’t know why. The salinity corrected alkalinity, nTA, is almost perfectly constant.
I found it interesting that the file has two independent determinations of pH: a direct measurement and indirect from bicarbonate and carbonate. The r.m.s. difference is 0.007 pH unit, so if the two methods are equally accurate, the standard deviation of each is 0.005 pH unit. Impressive.

“Salinity and alkalinity have a slight upward trends, I don’t know why. ”
Surface salinity varies from place to place in the ocean depending on the balance between evaporation and precipitation; excess evaporation leads to higher salinity, excess precipitation leads to lower salinity. If a given location in the ocean has a trend in the relative amount of precipitation and evaporation (whatever the cause of climate change), there will be a trend in surface salinity.
The ratio between alkalinity and salinity stays constant, since all salts are affected equally by dilution. So the trend in DIC has two components, one due to a trend in alkalinity linked to the salinity trend and one due to increased CO2. The variable nDIC has the first contribution removed.

The data selection is a major part of the story. What is as important, is Sabine’s reaction to questions put to him through FOI and the answers he gave. They appear to suggest they knew they were cherry picking data, but didn’t think they would get caught.

If the accuracy of 0.1 pH is a random error, large data set averages are more accurate. This is exactly the same issue as thermometer reading, where plus or minus 1 degree readings (and even large offsets due to urban heating or poor placement) were used to generate a data set claimed accurate to 0.05 C or so, with a total rise in 150 years of 0.75 C. Unless there is a shifting bias in the readings that is not corrected for, your argument falls on its face.

Leonard, agreed, but Berényi Péter has gridded the pH data in 5×5 degree boxes and he finds an essentially zero trend with an error margin over 30 years of ~0.02 unit/decade.
The measured (and theoretical) trend at a few places with modern equipment is around -0.015 unit/decade, thus not measurable with the pH glass electrode pH measurements.
The measurements in earlier decades were even more scarce and the trend smaller (CO2 increase 1850-1984 was about the same as 1984-current).

“However, it is a huge scientific resource, two million plus pH samples taken by oceanographers over decades,”
I remain puzzled how a mere 2 million bits of data cannot be analyzed in a short space of time by any of the groups with big computers.The new supercomputers in England could knock it over in 2 minutes, Mosher and Zeke 1/2 an hour, Nick Stokes or McIntyre perhaps a week.
Heck it could be a class project at any US university course on climate change.

Willis, regarding sampling density, I enquire as to why folks were measuring ocean Ph. I figure that there was local concern about the effects of industrial pollution on the oceans, thus programs to monitor closely the Ph were part of other environmental monitoring projects.
Japan, Baltic, Caspian and Black Sea?

Oceanography is important to Japanese that get a lot of their food from the sea. The Baltic, the Black and the Caspian seas are special cases which have aberrant and very variable conditions, hence interesting to study. The Baltic is brackish to almost fresh and very influenced by river runoff and occasional injections of salty water from the North Sea. The Black sea is unique (in the present) by being anoxic at depth while the Caspian is essentially a big salt lake. Incidentally, even in the deep anoxic part of the Black Sea, with a high concentration of H2S the pH does not go lower than 7.6.

Just saw Fabien Cousteau diving around the Great Barrier Reef off of NE Australia. He and Philippe Cousteau keep talking about the acidification of Great Barrier Reef etc. Looking at the average values of pH taken around that area Fig 2), it looks like it is among the most alkaline (pH 8.25). I wonder if those values were taken closer to 1910 or 2013? What are the pH values there now? Has it moved closer to pH 8.19 or 8.13 (or lower) now – that info should be available? Without time of measurements it’s hard to tell what’s going on between 1910 and now.

Probably not. The symbiotic algae in corals “eat” a lot of CO2 and keep the pH high. It can touch 9.0 in late afternoon over a coral reef. Lower in the morning of course, since photosynthesis stops but respiration continues in darkness.

There is no such thing as ‘an’ ocean pH. It varies diurnally, seasonally, and by ‘ocean ecosystem’ of which there are 8 in the Pacific. Swings are 1 to 1.5 annually, far more than theoretical possible AGW changes. Driven by biology, not climate. Essay Shell Games in ebook Blowing Smoke has referenced details. That is why we exist on a blue planet suffused by oxygen.

Can I assume then that you also don’t think there is such a thing as a global temperature? Temperatures also vary diurnally, seasonally, by latitude, by altitude, and for all sorts of other reasons. Perhaps you should let climate scientists know about the futility of their efforts before they make a fool of themselves. 🙂

Willis wrote: “What I suspect has happened is that the mass and complexity of the data was too overwhelming, and so the investigators simply put it into the “Too Hard” pile. But that’s just speculation, the real reason may be entirely different.”
My guess is that the real reason includes issues with the accuracy and quality control of the data. Glass electrode data are usually not much better than +/-0.1 pH unit, and can easily be much worse if proper procedures were not followed. So one has to sort through the two million data points to try to figure out which are really reliable, and most will likely end up in the “don’t know” pile. So I think it is likely to be “too hard” combined with “too little chance of ending up with something useful”.

Actually no pH measurements are ever much better than +/-0.1 pH units since they all ultimately refer to calibrations with a chemical standard calibration fluid. These are claimed by manufacturer to be exact to 0.01, but they aren’t. Even the best brands often vary by +/-0.05.

Thanks All for continuing to follow up and develop the WOD information.
I haven’t been able to post because of a technical problem. Also I haven’t wished to interfere, but at this point it seems there are many speculations that don’t match with the work I’ve produced on this nor do they match with the full history of my communications with the two PMEL authors.
Anthony Watts now has a copy of my transcript of PMEL communicaitons. Stephen McIntyre was given that transcript over a year ago if I’m not mistaken. Perhaps one of them will post. I don’t want that on my own site. Also all readers and writers may wish to examine the 11 posts regarding my own preliminary data extractions athttp://www.abeqas.com/category/ocean-ph/
Also it might be of interest to know that I covered these same concerns via several comments I posted at RealClimate last January (17?).. about a year ago. For some reason, there was no followup interest from anyone, but the comments are for the most part still there. Michael Mann was the guest host for that piece titled “if you see something, say something”. I’m grateful that they did not remove those comments but I hope they will sign the petition.
Also please note that the petition I produced was in response to indifference from every single subject matter expert and Senator that I took this up with discretely over many months. The petition only asks that NOAA do its job and develop this data properly. This way people like myself, Willils, and others, don’t need to take time out of our priorities to do their job for them.
Also, the petition doesn’t accuse anyone of fraud. If the PMEL authors of note were to sign the petition, that would be a good start towards reducing the heat on this topic and moving towards reform. Again the petitiion is at:http://www.ipetitions.com/petition/restore-the-worlds-ocean-ph-measurements

“Willis Eschenbach tips me to a story by Marita Noon, titled:
What if Obama’s climate change policies are based on pHraud?”
So now, a week later, not a fraud? If anyone is a fraud, I’m suggesting a particular grad student and his mentor both whom don’t vet their work before accusing people of fraud.

I told Anthony about the story, not because I thought it indicated fraud, but because I found it quite bizarre that a pile of data that big, 2.5 million observations made by professional oceanographers over decades, would just be ignored.
Note that the accusation of fraud came from Marita Noon, not from me. As I said above, I’m reluctant to ascribe motives. Heck, half the time I’m not sure what my own motives are until after the fact, and perhaps not even then.
w.

Do you have a problem with reading and comprehension ? Look at the comment from Mike Wallace at 7:46 pm … the very one prior to and, yeah, 10 minutes before your diatribe.

Streetcred, it’s totally unclear who the “you” in your comment is referring to. I suspect it’s trafamadore, but large oaks of contention grow from such small acorns of misunderstanding.
In any case, it’s very common for someone not to see a comment made ten minutes before theirs. Suppose I pull up the thread at say 9 pm. I then start reading it. At 9:15, I come across a comment I want to respond to. I spend another fifteen minutes answering it, including looking up references and getting a new cup of coffee. My response goes up at 9:30.
Meanwhile, there are an entire half hour (gasp!) of comments I haven’t seen that have been added to the thread.
So sue me …
w.

Follow the indentations, Willis. Had Trafamadore taken 30 minutes to compose and publish that rubbish then he/she/it definitely has an issue with reading and comprehension, so your explanation is in his/her/its case is weak. If Trafamadore had done any research into sourcing the original article alerting the pH issue then he/she/it would be fully aware that the author has been 100% ethical in how he has prosecuted his business. It is appalling that Trafamadore should accuse Mike Wallace “and his mentor both whom don’t vet their work before accusing people of fraud” … what does he think that they are, CAGW warmista?

Thanks, Streetcred. I don’t trust the indentations in the slightest, as they are difficult to follow. I and many others often reply at the wrong indentation level … heck, it’s not uncommon for people to post on an entirely incorrect thread.
That’s why I ask people to quote the words they object to, so we can have clarity about who and what they are disagreeing with.

Had Trafamadore taken 30 minutes to compose and publish that rubbish then he/she/it definitely has an issue with reading and comprehension, so your explanation is in his/her/its case is weak.

Thirty minutes was just an example, Street. In fact, all trafamadore needed was to take more than ten minutes to answer, and he’d have missed the new post … and I often go get a coffee or otherwise consider my answer, taking up ten minutes easy. Heck, I’ll often go off and read a few more comments, then come back to answer the earlier comments. So no, it’s not “weak” to think trafamadore might have taken ten minutes to answer … we’re not all as swift as you consider yourself to be, I guess.
So sue us all, I guess …
w.

Willis … “So sue me …” What an outrageous statement, are you serious or is it just the New Year cheer?

Streetcred January 1, 2015 at 10:08 pm

“So sue us all, I guess … ”
That is so immature … on what grounds do you suggest that this might be possible ?

On the grounds of humor … I picked up the phrase from when I was a musician backing up an amateur production of Guys and Dolls, but since then it’s gained its modern meaning, viz:

The earliest reference I can find is from the song ‘Sue Me, Sue Me’, in the musical ‘Guys and Dolls’. This was a Broadway show in 1950 and released as a film in 1955. This was composed by Frank Loesser and sung in the film version by Frank Sinatra (as Nathan Detroit) and Vivian Blaine (as Miss Adelaide):

Detroit: Serve a paper and sue me, sue me, what can you do me? I love you. Give a holler and hate me, hate me, go ahead, hate me. I love you.
Adelaide: When you wind up in jail, don’t come to me to bail you out.
Detroit: Allright already, so call a policeman. Allright already, it’s true, you knew, so sue me, sue me, what can you do me. I love you.

In the original stage version the line ‘you knew’ was given as ‘so nu’. Nu is a Yiddish word meaning (depending on who you ask) something like ‘what did you expect?’. This gives some weight to the suggestion that several American correspondents of mine have made – that the phrase is Yiddish and was in common use by Jewish men in New York prior to 1950. That would fit with the meaning of the line in the song. Loesser was Jewish, was born in and died in New York, and would certainly be familiar with ‘so nu’. ‘So nu, so sue’ is Loesser’s kind of rhyme and the jump to ‘so sue me’ being Yiddish isn’t a large one.
It wasn’t widely used until it was picked up again in 1990s America. There is a long running legal dispute between the Beatles’ Apple Corps and Apple Computer regarding trademark rights (1978 – 2006 and counting). In 1991 Apple Computer introduced a system sound into the Macintosh System 7 operating system – called ‘Sosumi’.
By 2002 we were seeing lines like this – in the ‘Humor’ column in the Maryland newspaper The Capital:

“Products today have too many features. I know I’ve said this before. So sue me.”

As the phrase gained popularity it began to be used in social situations and more often with irony than with belligerence. By 2004, the term was in use throughout the English-speaking world and had gained enough currency for the New York Game Factory to market a board game called ‘So $ue Me!’ – ‘An exciting new legal board game that turns litigation into a game of fun.’

Yes well. Readers shouldn’t HAVE to trawl through data to construct time series where prima facie an interesting scientific truth emerged from recent analysis showing a rising pH.
We spend literally $trillions. And if ocean acidification is disproven, that may be one of the most valuable discoveries in history.

What are you thinking? It’s simple physical and general chemistry. The partial pressure of CO2 goes up in the air (physical chemistry), more CO2 goes into the H2O (physical chemistry), the pH falls (general chemistry). Lot’s of details, like the temp of the water and the buffering in the water (both general chemistry) and where the water comes from (history, just kidding, Ill go with physics), but in the end it’s simple physical and general chemistry.

@trafamadore
You’re right – up to a point. You’ve written the first chapter of the story
If you did the experiment in the lab with pure water and CO2, you’d get the results you describe. That’s about as far as the theories of physical and general chemistry will take you.
But the oceans ain’t the lab and sea water ain’t pure.
The challenge for the experimentalists/observationalists is to show whether the expected effect actually happens in practice in the oceans where a whole host of other factors are in play (some of which you have mentioned).
The discussion to date show that they are nowhere near having enough usable real world data to adjudicate one way or another on the issue. Looks like they won’t have for a very long time either.
And even if there were shown to be a real world change in pH, it would be necessary to show that this actually mattered to anything we care about.
Personally I find it hard to believe that many organism couldn’t withstand a pH change of about 0.1 units. Any more than there are many which can’t cope with the temperature changes between winter and summer or between a week of low relative humidity and a week of high. Anything so highly adapted to a very narrow environmental range is unlikely to be widespread nor long lived (in evolutionary terms).

Strange, with all the talk of ocean acidity destroying coral reefs, no samples taken on the lower half of The Great Barrier Reef where all the fertiliser from agriculture and where the coal exporting ports are located, and very few from Mackay upwards, the same for Ningaloo Reef. it is almost like they were trying to hide something.

‘For the period from 1940 to 2009, corals from
both inner as well as mid-shelf sites exhibit the same overall decrease in δ11B carb of 0.086 ±0.033‰ per decade, equivalent to a decline in seawater pH (pHsw) of ∼0.017 ±0.007pH units per decade. This decline is consistent with the long-term effects of ocean acidification based on estimates of CO2 uptake by surface waters due to rising atmospheric levels. We also find that compared to the mid-shelf corals, the δ11B carb
compositions for inner shelf corals subject to river discharge events, have higher and more variable values and hence higher inferred pHsw values. These higher δ11B carb values for inner-shelf corals are particularly evident during wet years, despite river waters having lower pH. The main effect of river discharge on reef-water carbonate chemistry thus appears to be from higher nutrients driving increased phytoplankton productivity, resulting in the drawdown of pCO2 and increase in pH sw.
Coral records of reef-water pH across the central Great Barrier Reef, Australia: assessing the influence of river runoff on inshore reefshttp://www.biogeosciences-discuss.net/11/11443/2014/bgd-11-11443-2014-print.pdf
Does this help?

Willis: My Brother teaches “medical chemistry” at a community college in a large metro area.
Unlike my ERA when even at the University, you might have 2 to 6 students sharing ONE already 20 year old pH meter, at his school there is a pH meter for every student in the class, he intentionally gives the students one meter per 2, to enforce “teamwork”. None the less, he typically has 15 pH meters lined up, in FRESH 7.0, commercially made…buffer at the beginning of each pH usage type class. He looked at the previous measurements and comments and asked, “Who are these IDIOTS, and what experience do they have with instrumentation???”
He explained: 15 current (within 5 years) vintage, digital, self compensating (for temperature) pH meters, in commercial buffer solution. Line them all up, look at them 7.00 pH +/- 0.1 pH units. ALL THE TIME. Strangely (NOT!) you average them all and the number will be 7.0 +/- 0.07 or so pH units. It is NOT a self corrector type of error. (I.e., the central mean theory DOES NOT SEEM TO HOLD for this sort of measurement.
When he say claims to .03 or .01 pH unit accuracy by averages he SNORTED. “Meaningless”. I would tend to agree.

I doubt it is the meter that is the issue. More likely it is the glass electrodes. If you use cheap electrodes or if they have been mishandled (banged around, allowed to dry out) it will not matter how good your meter is.
It IS possible for careful, knowledgeable workers to get precision of 0.01 pH unit with NIST primary standard buffers: R.P. Buck et al., Pure Appl. Chem., Vol. 74, No. 11, pp. 2169–2200, 2002. But it is not easy.
The problem is that it is really easy for people to think they are getting that kind of precision when they are not even close. Which is why the historical data is likely to be pretty much useless.

Max,
Many thanks.
I think your post – with many others on this thread (and many others on this excellent site) – does indicate that the science is – actually – not settled.
There is a substantial (huge?) amount we simply do not know.
The oceans are huge.
A one degree by one degree grid square is – on the equator – 3600 square (nautical) miles in extent – that is 4 767.456 016 8 square statute miles – per http://www.onlineconversion.com/area.htm (bigger than Delaware or Rhode Island, and about 85% of Connecticut, or more than half the size of New Jersey; bigger than Cyprus, and about one third the size of Belgium).
And, forgive me, most of the non-empty grid-cells have one reading for pH, during 1910 to 2013.
Well, I guess we are a bit data-deficient.
Happy New Year to All.
Auto

took a quick look at the data:
1. most of the data is to 2 decimal places. I find it hard to believe that scientists would record pH to 2 decimal places unless they felt their equipment had that sort of accuracy.
2. I removed the outliers (ph 9), then plotted the average pH for zero depth by year, with no correction for lat long or season or girding, under the assumption that these are basically random noise by year and will cancel out.

ferd, what exact year is the outlier of just over 7.0?
At first glance I thought it might by 1998 which would make it both an outlier and a remarkable coincidence, but upon closer inspection it looks more like 1996 or 1997?

the first graph didn’t have the outliers removed. the second does.
here is the SQL I used. LT and GT replaced for HTML.
SELECT OSD_All.[Year], Avg(OSD_All.[pH]) AS AvgOfpH
FROM OSD_All
WHERE ((((OSD_All.[pH])) LT 7 And ((OSD_All.[pH])) GT 9) AND ((OSD_All.Depth)=0))
GROUP BY OSD_All.[Year], OSD_All.Depth
ORDER BY OSD_All.[Year];
[See correction below. .mod]

it late, corrected sql here
SELECT OSD_All.[Year], Avg(OSD_All.[pH]) AS AvgOfpH
FROM OSD_All
WHERE ((((OSD_All.[pH])) GT 7 And ((OSD_All.[pH])) LT 9)
AND ((OSD_All.Depth)=0))
GROUP BY OSD_All.[Year], OSD_All.Depth
ORDER BY OSD_All.[Year];

Unweighted averaging just gives you an average of a smallish region, heavily representing, say, the area around Japan. To give an idea of the poor spatial spread of this data, I counted for each year the number of 5×5° cells that had any data in each year. There are probably 1500 or so such cells covering eligible ocean (not ice, land).

I find it hard to believe that scientists would record pH to 2 decimal places unless they felt their equipment had that sort of accuracy.
You report the reading to one more decimal place than the accuracy of the instrument. Standard lab practice.

“I find it hard to believe that scientists would record pH to 2 decimal places unless they felt their equipment had that sort of accuracy.”
Sadly, that is not true. Give people a digital readout with 2 decimal places and most will assume that they have 2 decimal places of accuracy. Really careful scientists won’t, but they are a minority.

Surely the raw data should be captured as displayed. If others wish to ‘adjust’ it later, then at least there’s a full audit trail back to the original.
I think some guys in Norfolk (CRU UEA) got into a bit of hot water by omitting this step and just recording what they thought the instruments should have said. Bad ‘Science’.

Looks like there are a significant number of gridcells or larger combinations of gridcells where well populated time series of Ph can be put together for that area. If a bunch of these show similar trends, that would seem to provide pretty good evidence about the global trend, and this approach would not be very difficult at all.
Trying to optimally extract the global PH moving average from the full pile of data might be “too hard,” but taking a good first look at it should not be.

you could expand the group by clause in the above sql to include location, season. this would tend to isolate the trend at each location and season, and then you could average these all together for each year. SQL NULL handling should eliminate the need for infilling as commonly required in other techniques. No need to interpolate missing data. I’ll give it a quick look in the morning to see if it makes any difference.

If you put a layer where all the tectonical plates are shown above the sample’s concentration please note two important things:
Not only on the coast of Japan the Ph-samples are sampled in areas where there are frequent high techtonic activity and/or volcanos on the bottom. The activity of techtonic plates are one main reason for the sampling.
In the Baltic Sea there are two main reasons for sampling forgotten and/or not intended by those who use the usually tables for Ph-valuses:
* Due to an agreement back in time which is caused due to the problem of the Baltic Sea water being more or less poisoned the last Century, reasons all from “leaking” from industries, none or bad existing watercleaning to the number of leaking warships after WWII is one reason for a large number of samples among others taken by Naturvårdsverket in Sweden
* The water in the Baltic Sea lacks continued in-trasported normal sea water which has a higher value for Oxygen (the water in the Baltic Sea is usually said to be “brackish water”. Reason for all this can be found in one geological wellknown fact: Due to landrise still much higher north a line over from Varberg (Swedish westcoast over to close to Västervik (north Kalmar) the amount of water passing from the Baltic Sea out finally in the Atlantic Ocean, is as high as 10 000 000 000 cubic meters each year due to higher landrisespeec in the northern parts of Scandinavia (including the Baltic Sea)
South the mentioned line there is a landsinking.
This causes effects on the existing polluted sludge storage which in it self is a problem for the countries around the Baltic Sea.
All in all the places where no or only a few samples been taken are the majority of places around the world’s Sea systems….
Something to be better taken into consideration, I think….

Willis writes “There are, for example, about 400 1°x1° gridcells that have more than a hundred observations per gridcell, and groups of nearby gridcell cells combined have much more data.”
Maybe there are some grid cells that are adequately covered temporally to do a trend on? It’s only a sample but that again climatology does that all the time with proxies to get their historical global temperature trends….

Let me be clear that regardless of what this data shows, I think that the ocean is gradually becoming more neutral, at about 0.01 pH units per decade, as a result of increasing atmospheric CO2. This is most clearly shown by the Hawaii HOT time series of pH measurements.
But since in geological times the creatures of the ocean went through long periods of much higher CO2 levels than at present, I also think that this slight neutralization won’t make any difference to the creatures in the ocean. In the ocean, chemistry doesn’t rule life … life rules chemistry.
w.

Let me be clear that regardless of what this data shows, I think that the ocean is gradually becoming more neutral, at about 0.01 pH units per decade, as a result of increasing atmospheric CO2. This is most clearly shown by the Hawaii HOT time series of pH measurements.

I’ve witnessed some diplomats bowing simultaneously and successfully to opposite directions. Scientists should also stick to their own strengths. For example, some contributors here have already convincingly demonstrated the the infinitesimally small neutralizing impact on ocean pH of all atmospheric CO2 – let alone the about 4% human portion. There is very little to add to it, but perhaps the following:
The islands of Hawaii rise up to 13,675 ft (4,168 m). Much of the Pacific Ocean surrounding the state slopes down to 20,000 ft (6,100 m) deep. It’s pretty impressive and ever on-going. It seems hasty to exclude its temporary impact on ocean alkalinity* in the region.
*Assuming that an ISO 17025 accredited laboratory is willing to declare 0.01 pH unit accuracy even for the tested samples, let alone extrapolating beyond.

Hello Willis.
My understanding in this pH thingy is that it relates more to the climate than to the impact on life.
Of course there has being going on a much hypet noise about the danger to the life, but the main point is that it is about the climate.
The pH variation in the oceans is a significant pointer to the temp variation in the oceans.
Cherry picking a point in time and showing an oceanic temp picture for that time and then trying to imply forcefully that that must have been the case for a longer time period it does inforce a false perception and a falce (manufactured fact) proof of the oceanic temp variation, which by the way is very important to understand the climate, especilly in the last 150 years (the GW era).
The oceanic temp measurements may not give a good enough picture of the oceanic temp trend during the GW era.
The pH measurements and it’s trend may assist to a better estimation towards it.
As far as I can tell, the pH drop in oceans as served by the Feely and Sabine it implies that there has being a considerable absorbtion of CO2 from the oceans during almost all the anthropogenic CO2 emission era, meaning that the oceans were in a warming trend for all that time, as expected in a AGW scenario or a human-made GW.
The period of the significant pH drop after 1988, as per Sabine’s work, is not a long enough period to support in it’s own the claim of the “acidification” of the oceans. Actually the “acidification” (as a claim forwarded) implies (rather strongly) that even before 1988 the “picture” has been the same, a supossed significant pH drop, a warming trend for the oceans….aka AGW.
20 years is a very short time, even in the case of that sharp pH drop to reach to a conclusion that anthropogenic CO2 emissions is actually causing oceans acidification, unless implying and suggesting (rather forcefully and arbitrary) that that must be the case even prior……….and that sharp drop (as cherry-picked) means that it is good only for compensating for the time period of the “bad data”. In it’s own is good for nothing else.
As already accepted, by a very “good” reason for the cherry pick of data given……..as there was not a choice but to resolve to it.
The problem generally with “cherry-picking” of this nature is not actually the act itself, or the excuse about it one may give or offer, but actually what was done with it,…… for what purpose and for what motive…. is the real problem.
Served as a fact for gonverment policy is far to wide and long reaching……….not mentioning the whole media hype and noise……….
Sorry for going so long with this, only trying to explaing my own understanding.
cheers

Hello Whiten,
If the oceans warm, they will expel CO2 and the pH will increase.
What is measured is that more CO2 is dissolved in the oceans (total carbon increases) and the pH decreases, despite the temperature increase.
So I fear that you have things somewhat in reverse…
The main problem is that the real drop in pH is only 0.04 units over the past 30 years, so you need very accurate equipment which was absent before 1980…

@willis
Ummm.. I think the best you can say is that ‘At Hawaii, the ocean is gradually becoming more neutral’.
Generalising from just one series to ‘the ocean’ is going a lot further than the available data allows.
But I agree with your general point. Any organism so specialised that it can’t withstand a pH change of 0.1 units is going to be a very short lived one in evolutionary terms

Two short statements sum up the whole matter.
1. The glass pH electrode method has instrumental errors greater than the plausible variation in waters under test.
2. So do later methods, because of sampling problems.

Geoff, so do thermometers that read out to 1 degree C and had many bad locations, have possible errors larger than the variation. These were used over 150 years to claim a 0.75 C increase with 0.01 C accuracy. However, if the variations are random, better averages can be determined if sufficient numbers of samples are used. This applies also to the pH samples.

This declining productivity of the ocean leaves in seawater is not bound carbon dioxide, the solubility decreases to the temperature rise of the Ocean (about one degree Celsius since 1910). Excess carbon dioxide is emitted into the atmosphere and its increasing concentration in sea water results in acidification of the ocean.
Ocean productivity is decreasing due to its decreasing fertilization, ie. Decreasing supplies from the depths to the surface layer of seawater silicates, phosphates, carbonates, iron, etc. Elements determining the continuation of photosynthesis, carbon dioxide binding with seawater. Lowering the productivity of the ocean is the result of a weak fertilization. Poor content life-giving elements in surface sea water is in turn the result of cosmic processes, but let’s talk about this turn.
The ocean is a biological machine and her life depends on the mixing of water in its depths. The process is as yet poorly recognized and is now marked by a lack of knowledge about the processes of ocean water exchange. Since life in the ocean is endless, it is clear that there is a circulation of water in its volume. It is caused by the constant and variable gravitational influence of the Moon and Sun on the density of ocean waters varied. Ocean tides occur on the surface and in the depths of the sea. Dense and cold water deep sea bottom sediments containing particles (including life-giving elements and dissolved minerals), escape to the surface cooling and fertilizing it, and oxygenated water surface and sink into the depths where oxygen support biological processes. Additionally upwelling (rich in silicates, phosphates, carbonates), the surface changes its acidity by neutralizing it. Water exchange between the depths and the surface is intensified by the constant changes in the position of pole-changing inclination of the Earth’s axis. This causes a change in the centrifugal force acting on the inertial mass of water and its movement horizontally and vertically in the oceans. Changing the position of the poles are due to changes in the geographical position of the Earth’s metallic core mapped location change of the magnetic poles. The kernel of gravity moves in a fluid under the influence of external kernel variable Sun’s magnetic field. When heavy metal core inside the Earth moves the liquid outer core is a change in the position of the center of gravity of the Earth and changing the position of the axis of rotation. This results in the geographical position changes polarity and as a result takes place under the influence of a variable centrifugal force, inertial motion of ocean water and mixing them in a volume’s ocean.

Absolutely. If the consensus trend is correct, the oceans are becoming more neutral, and would have to pass through a point where the water is perfectly pure. Only after that could it be described as ‘acidic’. Currently the oceans are not acidic in any shape or form, and therefore they cannot be undergoing the process of acidification.
It seems to me that everyone is bending over not to use the word ‘fraud’. The authors decided to delete a vast amount of data, presumably without a scientific proof of this in their paper. Simply to call the data ‘unreliable’ or whatever without proof is completely unacceptable.
Of course, by cutting off the data at 1988, it is almost certain that they are giving a completely false picture. Mike Wallace’s reconstruction in the other thread shows that, despite a fall since 1988, since 1900 there is essentially no trend. ferdberple’s average from the data shown above possibly shows a positive trend over this period (becoming less ‘acidic’). It also shows a positive trend in the last few years.
If these reconstructions, however preliminary, are correct, then the result is astounding. It means that pH has been changing in a natural cycle over the last 100 years, and there is no increasing ‘acidification’ that could even remotely be linked to CO2.
It has been rightly said that ocean acidification is the last refuge of the scoundrel.
I call it more than that. I call it scientific fraud.
Chris

Chris, Mike Wallace’s compilation of the data doesn’t show a global or even local pH trend. It shows the average of each year of pH measurements taken at very different places and different seasons with an equipment that can’t measure the faint change in pH caused by more CO2 in the atmosphere.
It is the same as lumping the temperature data from all station above 30N together one year and the next year mainly from stations between 30S and 30N and then conclude that the atmosphere is warming…
The modern measurements since 1984 do show a small trend of 0.04 pH units at all open ocean places and repeated ships cruises if looking at the same places and the same season over time.

You discarded 2% of readings because they were ”outside the normal pH envelop”. But those figures are an average of the pH data not a true average of the oceans as a whole. There are regions where pH is 4-4.5 but you would have discarded those perhaps. Those discarded data must be inspected for position, date, time, and depth.

Any data on pH is of value. If we had only a couple of dozen samples of the ocean spread over all of them, we could at least say the ocean is a bit variable but it is around pH8. If we were sampling the ocean on Titan and we had only one site to select, could we not feel confident that it was a hydrocarbon sea and probably, because of the ‘hydrocarbonological cycle’ that the whole works was hydrocarbons?
I already see something interesting. The lower pHs around the continents and particularly in the polar regions – means something? Also pH does vary with temperature a little bit (but the reverse of what we see in polar waters -pH up with Temp). Also major rivers lower pH locally, probably why continent margins seem to have lower pH. Also, pH on the ocean surface would be affected by heavy rains. I like the 1metre samples better.
A lot of confounding complications. However, I think taking all samples in decade bins for 1910 until the present decade should give us a reliable enough trend to see if pH has been lowering over a century. By the way, what was the average? Let me guess….Hmmmm I’d say pH 8.

There is a whole wing of regulation that punishes people and businesses of all sizes for misrepresentations related to omissions of material fact. This one seems pretty glaring and material. You usually don’t get the people going on record as to intent as apparently also happened here. Not as fraudulent as a hockey stick, but still possible to at least get charges filed in a different field of endeavor. Leaving large amounts of data out without addressing it prominently and in full should automatically seem reprehensible to a scientist trying to do honest science.
Even preparers of a mutual fund prospectus know you have to highlight important caveats +and prominently+ in order to not be misleading. Using selected data that raises an alarm seems no different than using selected data that exaggerates investment performance. Not to mention the pretense of prediction that accompanies every press release if not every “study”

Willis, I’m sure you have this under control already but I think this is interesting. If we look at the number of measurements by year we see that after year 2000 we essentially have the same low frequency as in the 1930s. There is huge drop off after 1990. I haven’t look at how this affects the different grid cells, I can only assume that the coverage is still the same but redundant measurements in nearby areas are no longer done to the same extent. So possibly, your coverage graph may be sligthly missleading.

here is a plot of the raw data, between pH 0 and 14. As can be seen there is a likely data quality problem in the mid 1990’s that would likely skew any trend to show “acidification”. There is also a similar problem in around 1960.http://oi60.tinypic.com/21do9qd.jpg

As for a trend, looking at the graph of raw data immediately above, the mark 1 eyeball says there is no significant trend likely to be found in the data. It looks pretty much flat line from 1910 to present. pH starts slightly above 8, and ends slightly above 8, and doesn’t show any significant pattern trend above or below the line.
Yes if you correct for location, season, and sample density you may be able to narrow the spread of the data and find a trend, but there is also a good chance of introducing a spurious trend.

Ferd, the theoretical trend from increased CO2 levels is 0.1 pH unit since 1850, of which 0.04 pH unit since 1984. You have definitely proven that the glass electrode pH measurements are too inaccurate to show any trend in any direction. Thus the answer of Sabine was right: insufficient quality of the data.
Except if you can combine samples at the same place and season over time, but even then…

Ferdinand by your logic the glass thermometers used to create a statistical record of average surface temperatures cannot work either.
However, that is not correct, because statistics can be used to combine many inaccurate samples into 1 sample of greater accuracy.
What I’m seeing that the underlying data has no trend, because the trend = 0, not because the equipment is inaccurate, but because the data shows that acidification is not happening.
Thus, the data shows that the theory that human activity is acidifying the oceans is contradicted by the data.

Fred
Not so. Whilst a stastically meaningful result can be gained where, for instance, there have been seven readings of a thermometer at the same place and the same time, by discounting the outliers and averaging the rest, in reality that doesn’t happen as there is often just one reading. No matter how much you massage it, should it turn out to be inaccurate,, a bad reading is a bad reading .
The same applies to ph readings. If numerous ones were carried out in one place at the same time I would accept you can extract meaningful data from it. However, I suspect these are highly random readings and their value in part, if not in total needs to be queried.
Tonyb

Tony,
It is even worse for the pH readings: the samples are not even taken at the same place and in the same season… That can give differences of up to 1 pH unit from one year to the next, depending of where and when the weight of the samples was in each year. While one is looking for a trend of 0.1 unit over 160 years…

Nicely done Ferdberple (and others). I think your independently developed time series is consistent with my plot which has been featured in Anthony’s first post on this topic, given that your plot covers all records and that particular plot of mine filtered out all records from depths greater than 200m.

My conclusion looking at the data is that the explanation that it is not of sufficient quality to calculate a pH trend is without foundation:
To the degree that the pH readings are “random” as to location and season from year to year, and the underlying data is bound by the central limit theorem, it can be argued that these readings are simply random samples from a population, and will be normally distributed around the mean for that year, and can be treated as such statistically.
While the above is unlikely to be strictly true, because weather, human populations and geography will favor some areas; weather, population and geography themselves are essentially random.
There is a danger that gridding and infilling will simply create false trends where no trends exist, because it will give significance to areas where data is sparse, and remove significance from areas where data is plentiful.
If there is a real trend in the data, it should be somewhat visible to the eye in the raw data without the need to torture the data to gain a confession. I’m not seeing any sort of trend in the raw data.
I do think however that the data shows more than enough data quality to calculate pH trend (or lack of trend), as aside from some obvious data quality problems, the data shows reasonably tight grouping. It isn’t scattered all over the place as it would be if it was low quality and/or high noise.
Thus, my conclusion looking at the data is that the explanation that it is not of sufficient quality is without foundation.

ferdberple.
You do not get it do you! 🙂
The data that do not support or comply with the theory is not good data, or as they say lately is of no sufficient quality.
There is no buts and ifs there……… theory first then data but only if data supports the theory otherwise it becomes junk data….or worse it gets lost and destroyed in the process of the hockey-sticks and cherry-picking .:-)
I think you have already heard and know about the 97% consensus and the 95% certainty on the theory, whatever theory that is….:-)
The latest and improved modern-day climatology. 🙂
Ferdinand has being telling you that for some time now.
cheers

Ferd, as far as I remember from very long ago statistics, you can obtain meaningful results if the sampling is representative for the whole population. In this case there is a huge oversampling in 10% of the areas and near no samples from other areas.
That is as representative as looking for the average height of people on earth where your sample is 50% composed of people from Scandinavia and the rest scattered over the earth and practically none from South America and Asia…
All what one can do is looking at binned data within one small area and the same seasons and look at the individual trend at that area. Eventually combining them by removing the local and seasonal offset.shows more than enough data quality to calculate pH trend
Sorry, even after throwing out the worst outliers, the whole cloud is between pH 7 and pH 9. Accurate measurements (colorimetric and calculated) since 1984 show a seasonal variation of 0.05 pH unit (Hawaii) up to 0.1 pH unit (Bermuda). Trend in several places: ~0.04 unit.
Are you really sure that the glass electrode data are accurate enough to show such a trend?

I would question that the readings are necessarily random by season. They might be over much of the planet, but both the arctic and Southern oceans can get right cranky as you move into winter. There’s a reason that many field scientists talk about “field season,” and it is all about climate. This may in part explain the sparsish data around Antarctica.

‘two million plus pH samples taken by oceanographers over decades’
Sounds like a lot but lets us look at that again , its over decades so it reality even an yearly average for limited area not be possible and the ocean is two thirds of the planet with some areas having no or little coverage . so the actual amount of coverage for any area is actual not much. And the old trick of ‘smearing’ the data over a large area is hardly one that can be accepted without question.
The problem remains the data is used not because its know to be a good representation of what is being measured , but be because its ‘better than nothing ‘ So in one way not using can have a degree of justification, the trouble is they replaced it with worse model run ‘data’ with all the problems that brings and simply have not made it clear why this real world data was rejected in the first place and given the authors own backgrounds and former publications , the temptation to get the ‘right’ has opposed to a honest result can be seen has one they may well have fallen for.
Once again in climate ‘science’ we see the professionals working at a standard unacceptable for an undergraduate , the rejection of real life related data without explanation of reason. And once again we can ask , is there actually any standards in this most politicised of ‘sciences’

My greatest take from this post and the comments so far is this by our apparent resident Oceanography expert.
“Ferdinand Engelbeen December 31, 2014 at 6:44 am
The pH drop is mostly near the surface, as the exchange with the deep oceans is very slow. But is measured since 1984 (-0.04 pH unit)”
So as with the so called “Global Temperatures” we have a POSSIBLE change over 30 years that is minute in comparison to that which the earth experiences on a daily & annual basis and which humans (and probably all sea creatures) cannot even detect.
And just like with the temperature the Warmists want to waste Trillions to offset for a Possible change of 0.12 pH unit over the next 100 years and that is only in the top 200M of the Oceans.

AC, where in the life of WUWT have I ever said that the minute temperature increase over the past 100 years or the 0.1 pH unit decrease will have any negative impact?
Most sea creatures (coccoliths, corals) evolved in much higher CO2 levels and temperatures.
But my stance is that you can’t lump a lot of inaccurate pH data of different places and different seasons together and call the result a “trend” of ocean pH…
As good as you can’t do that with historical CO2 data measured by wet methods in the middle of Paris or forests or temperatures in growing towns…

your result above for japan is a cherry pick. it is statistically insignificant.
the brute force result previous is essentially a random sample. so long as the data is bound by the central limit theorem the results should be “good enough” to at least get us in the ballpark and tell us if there is anything significant to be found.
As Berényi Péter results below confirm.

There are a whole lot more Chinese peeing into the rivers that flow into the oceans south of Japan that there used to be. Not only is this causing the oceans to rise (biggest increase in sea levels are in that part of the world), now we have proof they are acidifying the oceans as well. Hopefully the UN will get a global agreement for everyone to stop peeing before it is too late.

have you stopped to think about what the graph actually shows? 3 reading, each almost 700 miles apart on the ocean, with different currents, different rates of evaporation, rainfall and photosynthesis. each with different pH but EXACTLY the same slope on the graph.
And you don’t think to question? Have you ever seen 3 experiments in science, conducted at 3 separate locations, deliver exactly the same results? Almost as though the experimenters were in communication with each other.
and then stop to ask yourself, in ocean pH is such an issue, why does life not die off every day and every year, given the change in pH due to location and season? the measurement is a nonsense, and the fact that three locations deliver the exact same result over 35 years.shows collusion.
you wouldn’t believe this result if three locations showed EXACTLY the same trend for temperature, rainfall, or any other physical measurement. you would think they were cooking the books. yet you accept if for pH to what, something like 1 part in 1 million? because to my eye that appears to be how similar the slopes are. the data is not believable.

Wouldn’t an obvious explanation be fertilisation in coastal waters from run off? Having dived quite a bit at various world locations I can assure you that I see far more algae on reefs today than I did 30 years ago…

If anything, the trendline in the raw data shows that the surface is becoming less acidic, which would explain why the atmosphere is showing more since 1910. As CO2 has been driven out of the oceans into the atmosphere, the ocean pH is increasing, as is the CO2 ppm in the atmosphere.
So, if anything, the raw data is consistent with the theory that the increase in atmospheric CO2 is not due to human burning of fossil fuels. Rather, it represents a loss of CO2 from the oceans, due to a process that is evidently not yet well understood by science.

Sorry, impossible: there is an increase of total carbon measured in all open oceans over time (lots more accurate measurements than pH). That is because the oceans absorb part of the increase in the atmosphere, not the other way out.
If the oceans were a net source, and humans add twice the amount as found in the atmosphere, where does the rest go? into space? Not in vegetation, as that only absorbs some 10% of human emissions (as proven by the oxygen balance).

Ferd,
Berényi found an overall trend of -0.002±0.038/decade for pH measurements
The Japanese found a trend for specific places of -0.015 to -0.018±0.003/decade
As far as I can see, the data of the Japanese are widely within the error margin of what Berényi found, but with much better equipment.
But you haven’t answered my question where in nature the sink is that removes halve the human emissions + all the extra CO2 alleged to come out of the oceans?

Latitude, CO2 was never a limiting factor in the oceans, trace elements (iron) are the limiting factor.
During spring in Bermuda including algal blooms, DIC (mainly bicarbonate) drops with 2.5% in seawater. That is all.

Latitude, CO2 is one of the limiting factors in the atmosphere, it is not a limiting factor in the wide oceans.
Total carbon (DIC), of which over 90% bicarbonate, the building block for most shells and corals, at Bermuda in winter/spring: 2060 μmol/kg in summer/autumn. After several algal blooms: 2030 μmol/kg. Doesn’t seem that algae are starving from bicarbonate shortage. But the change in DIC by algae has a huge influence on pH and pCO2.

Land plants can get all the CO2 they need by opening their stomata. CO2 supply is limiting when the plants have to restrict stomatal opening to limit water loss by evaporation. Not a problem for marine.

A preliminary look at the data shows beyond doubt, that ocean pH is decreasing indeed, at a rate of -0.002±0.038/decade. In other words, it is absolutely stable.
(5×5 deg grid boxes, monthly averages, trends computed for grid box/month combinations with at least 15 years of data – 382 such boxes were found)
If only grid boxes with at least 20 years of data are considered (204 items), ocean pH trend is -0.002±0.031/decade, therefore the null result is reasonably robust.

As the measured (and theoretical) trend in several places is about 0.013 pH unit per decade, that still is largely within the error bounds of the overall trends.
Maybe an interesting question: can you look at trend of the 20/30 years after 1989 of the grid box where more accurate measurements were done like Hawaii and Bermuda?
Bermuda was/is sampled at two places:http://bats.bios.edu/bats_location.html
Hawaii deep ocean measurements are done at 22 45’N, 158W, 100 km north of Oahu.

Yes, but when you average multiple samples and at the same time note temperature can you not compare readings at the same site? Did the pH electrode report proton activity or not? Or are you proposing that it is fundamentally impossible to ever measure pH to within 0.1 pH units?

-0.002±0.038/decade
==========
that shows a very close match with the raw data brute force plot. well within the error bounds.
which is in itself interesting because it confirms that for all the gridding and infilling that is done to try and compute “global” averages, alarm bells should ring if the “corrected” result shows significant statistical difference from the raw data.

Ferd and Latitude,
Have a look at the original “trend” of Wallace for the past 30 years: that shows a drop of 0.3 pH units, which is widely outside the error margin per grid found by Berényi Péter.
So can we agree that the compilation by Wallace doesn’t show the real trend (whatever if that is zero or very small)?

James Harlock,
Agreed! The problem is that Ferdberple and Latitude still think that that rejects the few series where the accuracy of the measurements is much better, but still think that a “trend” with glass electrode pH measurements has a meaning…

Latitude, agreed, one can never know what somebody else really thinks, I sometimes don’t know it from myself…
But I like to know your current thoughts about the pH “trend” compiled by Wallace and the general possibility that glass electrode measurements can show a decreasing trend in the order of 0.015 pH unit/decade over the past 30 years…

“I always love it when I see a supposed rate of change that has an error of +/- 1500-1800%.”
Yes. That’s what you get from the Mike Wallace data which Feely is criticised for not using. For the Hawaii data he did use, the trend was 0.0188 +- 0.0022 /decade.

“1. Period of stabilization of the magnetic activity Sun.
2. Stabilization period earthly pole position.
3. Descending upwelling in the ocean causing a decline in their photosynthesis and warming seawater.
Reducing CO2 solubility in seawater as a result of heating surface ocean waters, reducing the absorption of CO2 in the process of photosynthesis, increase the content of CO2 gas in the surface waters of the sea due to the increased acidity, decrease absorption of CO2 from the atmosphere and gradually increasing the concentration of CO2 in the atmosphere by diffusion of excess CO2 from seawater into the atmosphere to a level of 300 ppmv over the duration of about 20 000 years Earth’s poles traffic loss and the consequent warming ocean waters about 12 ° C and warming the Earth about 12 ° C.”

Robert,
Interesting claim in your link:
“…discovered the startling fact that corrosive waters were at acidic levels not predicted by climate change models to occur for decades.”
I wonder if Feely has any evidence to support the claim that the waters were at the acidic levels?
Does he believe it is accurate?

I am sure that the Heinz foundation only supports research that they like, but that doesn’t imply that what Feely, Sabine and a lot of others have done is false. Feely and others did a lot of other ocean research than pH alone.
And as Berényi Péter has shown, the margins of error from the glass electrode measurements are larger than the trend measured/calculated over the past 30 years. Thus Sabine was right to reject all old pH data made by glass electrodes, as these can’t show the (theoretical) trend…

Thus Sabine was right to reject all old pH data made by glass electrodes
===================
by that logic we should also reject glass thermometer readings, which have been used to calculate a 0.6C temperature change over 100 years.

Ferdberple,
If the margins of error are larger than the trend, then it is impossible to conclude anything from the data. That does mean that the historical pH data are worthless to deduce the real (calculated) pH trend. That doesn’t mean that the data are worthless for other interesting items, as they do give some information about pH distribution over latitudes and seasons, which are much larger than the trend.
But you can’t deduce a trend like Wallace has done from these data and then accuse the researchers of “pHraud”…
I don’t know what the margins of error are for temperature readings, but as that are much more data from a lot more places, the overall error may be smaller, although other problems may arise (UHI, number of stations, change in equipment,…).

“EPOCA was the first international research effort on ocean acidification. The 27-member consortium put many other processes likely to be affected under the microscope. These include nutrient uptake, reproduction, acid-base regulation, nitrogen fixation and primary production. Changes in the dynamics of these biological processes are likely to affect marine flora and fauna profoundly.
The four-year long project produced results based on four themes. One of the major findings under the first, ocean chemistry, is that acidification measured in terms of pH drop in the Arctic near Iceland is 50 % faster than average rates in sub-tropical zones in the Pacific.
Project researchers coupled Earth system models (ESMs), global and regional ocean models, and a sediment model to anticipate how acidification will alter ocean biogeochemistry. Climate change has little effect on acidification except in the Arctic, where freshening from ice melt exacerbates the situation. Regional model simulations highlighted the vulnerability of some near-shore regions as a result of river input and organic matter degradation as well as local upwelling systems.”http://cordis.europa.eu/result/rcn/85717_en.html

“The same growth mechanism of carbon dioxide content atmosphere occurred by the IPCC (1997 Report), between 120-130 thousand. years, which means that no it could cause a man and his civilization. It is therefore necessary to look for another explanation of the reasons temporary increase of atmospheric carbon dioxide, perhaps such as that proposed above. Climate change, changes in carbon dioxide emissions from the ocean are therefore a side effect of changes biological productivity of the ocean. It is controlled by cosmic processes already described by many researchers, including by Milutin Milankovitch. Warsaw, 25 October 2013, amended on February 6, 2014 year. ”
Bogdan Góralski

“Among the relatively large number of phytoplankton species occurs only a few in amounts that indicate their dominance across the whole Baltic Sea. Generally meet the spring diatoms Chaetoceros Achnanthes taeniata and wighamii and dinoflagellates Peridiniella catenata summer cyanobacteria Aphanizomenon flos-aquae and Nodularia spumigena along with various kryptofitami, and in the autumn diatoms Coscinodiscus granii and Thalassiosira baltica and Rhodomonas kryptofita minute. In winter abundance of algae is very low, and the propagation of very weak or non-existent. In the spring, when it is more more sunlight and the water warms up and is it enough In- żo of nutrients, diatom bloom starts and immediately after the dinoflagellates and various small flagellates. In summer, the phytoplankton is dominated by blue-green algae, and in the autumn diatoms again.”http://ocean.ug.edu.pl/~oceju/CentrumGIS/dane/morze_baltyckie.pdf

What appears to be pHraudulent is the term “ocean acidification”. It implies nasty acids are going to burn us when we go swimming. The oceans are alkaline (pH around 8) yet we going swimming in rivers and dams that may well be slightly acidic.
The largest variety of aquatic animals prefer a range of 6.5-8.0.
Of course Wikipedia has its usual CAGW/CC/CD correctness: “The pH of seawater plays an important role in the ocean’s carbon cycle, and there is evidence of ongoing ocean acidification caused by carbon dioxide emissions.”
Where is the peer reviewed literature that predicts that the oceans will reach a pH<7.0?

The Warmistas have no other interest in the pH of seawater, other than the to be able to predict the future ocean as a hot boiling acidic catastrophe maelstrom. CO2 present in sea water is 99% a bicarbonate, with barely 1% of it present as carbonic acid These strange people are only interested in fooling the population into believing their weird theory of CO2 being out of control.

I keep hearing that glass based pH electrodes are too unreliable to measure pH to better than 0.1 pH units. That is completely incorrect, such inaccuracy is only seen in low conductivity solutions -which is NOT the case for seawater. My lab routinely measures pH to +/- 0.02 pH units with a combination electrodes and quality assurance is easy using calibrated buffer solutions (NIST traceable). The bad measurements seen in the raw data presented above are probably data entry errors and/or human error. Rejectin all ealy data is patentenly absurd.
HTH

Mark,
Have you systematically studied sea water that is in situ v. days to weeks after sampling? The effects of ussing containers of various compositions? Effects of filtered v. unfiltered? Filtered with fine v. coarse filters? Biologically active v. killed biota? Sampling the top mm, 5mm, 10 mm etc intervals? Noting high temperature gradients over such intervals, esp in still waters? Day v. night measurements? And the factorial combinations of all of the above?
Yes, you are claiming an accuracy for the glass electrode, but you cannot use that accuracy for past times when many of the above are known unknowns.
Sea water is moderately high in ionic strength and needs consideration of effects such as Debye and Huckel described. It commonly has suspended matter that can cause insidious instrumental drift. It commonly has biological activity that can do likewise.
The holistic accuracy is far worse than lab accuracy, rendering not only the glass electrode methods unreliable, but also other methods. If you have ever studied sampling theory for earth science systems, you will be aware that sampling the oceans as has been done, involves large errors irrespective of how pH is measured.
(I wrote a draft Masters’ thesis about relevant electrode complications).

same problem we face with glass thermometers. yet we don’t hear scientists crying out that we should scrap GISS and HADCRUT data in favor of the much more accurate RSS and UAH satellite data. scientific hypocrisy. cherry picking from start to finish.

None of the above affect the pH except ageing the sample, the glass electrode rejects all except protons which is why it works in the first place and is used to measure the pH of sewage ! Do your accept that a Nerstian slope is proof of the principle? A dye method is FAR less reliable in the presence of organics.
HTH

Hmm. I’m sure you could get a Masters from talking about lon known effects on glass pH electrodes. But, you chuck a bucket over the side of a ship, and dip a glass pH electrode in it and note the temperature. Simple, repeated thousands of times and perfectly acceptable. Yet you want to contaminate it by storing, filtering, heating etc. and then using a dye? That complications can be introduced by ‘scientists’ is yet another example of ‘post modern science’ IMHO and assume that all the giants on whose shoulders you stand were idiots. Let me throw your complication back at you, for all reasonable variation in ionic strength of a fresh sea water sample how much would pH be altered?

ferdberple,
Your plot of all the raw data (minus outliers) tells the story accurately given the large amount of data points. It is an excellent presentation of the data without any statistical manipulation. Given the large number of data points it is surprising to me that anyone would raise the question of the accuracy of the instruments given the accuracy stated up to 0.1 pH units (which has been questioned as too large). The trend is important.

The accuracy of the instruments is important when great levels of accuracy are being claimed for the results . You want to claim your results are correct to 0.01 then you better have a means to measure to at least that level. To often we see the notion that we can get greater levels of accuracy by ‘throwing enough maths at it ‘ than the means of measurement is capable of doing . And is before we get to error margins , real life has opposed to lab life , how instruments change over time, how the instruments are used etc.
Oddly there are reasons to take real data with a pinch of salt , for various reasons climate ‘science’ is rampant with this issue , however that does not mean you can just use ‘model data ‘ instead , especially when you fail to mention you did this. In this highly politicised area where many of its leading lights have done much to earn mistrust , you can see why such actions send up red flags to others.

Gents,
I take a bit of issue with the bandying about the glass electrode. While those in school kits are questionable for low alkalinity water (semiconductor rinse water or subcritical+ utility boilers feeding steam turbines), they are decent for environmental work.
In my line of work I use a variety of qualities in pH measurement equipment. When the field instruments are calibrated on a 2 or 3 point scale with quality buffers, the accuracy will be within +\- 0.01 units. Now, if I take a sample of condensate (re-condensed steam after the turbine) and try to stir it in a beaker and measure the pH, I am wasting my time because a generic probe will not stabilize until the sample has absorbed atmospheric gasses overwhelming the few ppb of ammonia until it stabilizes at around a pH of 5.65 and its conductance is about 0.65 mmoh (uS/cm). We measure contaminants in single and double digit ppb’s. At those concentrations of buffering agents (NaOH, phosphates, ammonia or amine’s), and the pressures (700 psi to 4000 psi) and temperatures 300F to 1150F, it takes very little acidic ions to wreck our equipment. We must measures pH correctly day after day, year after year. Back in the 60’s and 70’s, the industry worried about carbonic acid. We can measure this using cation resin separation of basic ions from anions. The resin releases a hydrogen ion for each cat ionic molecule it takes up. The anions in the sample will associate with the H+ to form the conjugate acid. Acids will give water more conductance than bases. This is known as cation conductivity. Today we know that CO2 will combine with the ammonia to form a non-ionic ammonium carbonate which is ejected in air removal equipment. There is also no supporting evidence that it causes damage. Again, this is in an ultra pure water.
in the job prior, we measured “fresh”water. I quote fresh because the water was taken from near the end of the Brazos River west of Houston, Texas. It has received the effluent of municipal and industrial discharges all along its course. We stored it in a 700+ acre reservoir prior to treatment. The pH of this water would swing a full unit of pH in a 24 hour period. Rainfall and changes of wind direction, seasonal biological activity which will take and release chemicals from/into the water would change the pH in shorter time frames.
Remember what pH is, power of the Hydrogen ion. But also remember that it is not just the H+ that contributes to the acidity or basicity of water.
In seawater, a change in a few ppm of the very weak carbonic acid ain’t going to do much. The ocean is an open system of unimaginable volume. i personally find it difficult to imagine a few more ppm of CO2 in a buffer as strong as seawater will have detrimental affects.

The statistically significant results point towards seawater pH to be 8 and constant – even at river runoff. Or what else would explain the reduced measuring frequency since 1982? An alarming signal detected from the noise would have surely justified more monitoring resources even then.
In my opinion omitting the results is a serious mistake and can be attributed to fraud, ignorance, stupidity and/or incompetence. The more climate scientists reveal, the less likely fraud seems.

I presume that for the last 100 years individuals researchers have been taking seawater from different locations , filtering to remove biological organisms and silt , and checking the pH with careful changes in ambient CO2 partial pressure and temperature . It seems an obvious series of experiments to do and could be carried out with little expense anywhere.
It must be written up in the standard ocean chemistry textbooks .
S what did they find in these artificial controlled experiments , did the results agree with theory?

All,
One of us needs to find region(s) with substantial density of surface pH observations over an extended period of time (as long as possible, of course) and determine the temporal variability over that period. What is the interdecadal variability and long-term trend? My intuition is that Feely et al did not secure the full story by only looking at a short period (20 years). This is really important work that some of us need to do…cliff mass, university of washington

Cliff Mass:
Agreed that perhaps more work on this unique dataset could be useful. The Website refers to many more parameters than pH that were collected on these cruises, including temperature, salinity, and several carbon measures such as pCO2, etc. Some of these can be used to estimate pH theoretically, and thus would be excellent quality control checks. I tried downloading the data with a few of these variables and successfully received the full dataset (2.4 million lines) in about 10 .gz files. However, the files require more post-processing than I am used to, because each set of data is accompanied by metadata on the cruise itself (NODC Cruise ID), date, time, etc. before the rest of the data appears in normal spreadsheet fashion. Also I had only checked off a few variables instead of the total number that would best allow for analysis of both the carbon chemistry and other ancillary variables.
It would be great if you could get a graduate student involved in investigating the database.http://www.nodc.noaa.gov/OC5/SELECT/dbsearch/sysinfo.html

Cliff
Have you asked John Kennedy at the British met office? He compiles the SST data for Hadley and will possibly know related ph readings which may well have been done by those royal navy and scientific expedition vessels that came up with the best of the SST readings. Many of them are not worth a light I believe, for a variety of reasons, and John knows my opinion on much of the historic sst database ( pre 1955)
However, there are certain areas and certain timescales where the data is relatively robust.
Also, did the Challenger take ph readings? Those are probably worthwhile as the oldest ph readings of integrity.
Tonyb

One of us needs to find region(s) with substantial density of surface pH observations over an extended period of time (as long as possible, of course) and determine the temporal variability over that period.
========
see:
Berényi Péter December 31, 2014 at 8:58 am

I think that the many pH readings taken in the Caspian Sea do not represent what is happening with the oceans because the Caspian Sea is the largest landlocked sea, with no connection to the oceans.
Also, I noticed that the highest sample densities are often near areas with a lot of industrial and economic activity, and water pollution can affect pH readings. pH readings in those areas can change from increase of industrial activity or prosperous population, and change again from enactment of laws that restrict water pollution. If a dataset is created with all grid cells of the oceans having equal weight instead of all samples having equal weight, I suspect that will tell the story of global ocean pH trends.

If a dataset is created with all grid cells of the oceans having equal weight instead of all samples having equal weight, I suspect that will tell the story of global ocean pH trends
=============
see:
Berényi Péter December 31, 2014 at 8:58 am
and
ferdberple December 31, 2014 at 8:29 am
both approaches generated near identical results.http://oi60.tinypic.com/9s7xvo.jpg

Comparing the following Attribution focused Logic Constructs:Logic Construct ‘A’
– Premise: decreasing the temperature of seawater causes pH of seawater to decrease
– Argued observation: the pH of seawater is decreasing
– Is the temperature of seawater decreasing?
– Arguably we do not know the temperature of seawater sufficiently to answer.
&Logic Construct ‘B’
– Premise: increasing dissolved CO2 in seawater causes seawater pH to decrease
– Argued observation: the pH of seawater is decreasing
– Is the dissolved CO2 in seawater increasing?
– Arguably we do not know the dissolved CO2 of seawater sufficiently to answer.
John

About logic construct B:
There are far more abundant and more accurate measurements for DIC (total dissolved inorganic carbon) than for pH.
All series taken at the same place over time show an increase of DIC in ratio with the increase of CO2 in the atmosphere.
A gridded overview would show that over all oceans…

Ferdinand Engelbeen on January 2, 2015 at 4:07 pm
“About logic construct B:
There are far more abundant and more accurate measurements for DIC (total dissolved inorganic carbon) than for pH. [. . .]”

Ferdinand Engelbeen,
Comparing the two Attribution focused Logic Constructs ‘A’ and ‘B’.
How can there be more seawater dissolved CO2 measurements than seawater temperature measurements and therefore how can there be sufficient dissolved CO2 measurements if there are insufficient temperature measurements? Logically necessary and sufficient answers accepted.
John

I’m curious what could cause the nodes of blue in the ocean surrounded by a sea of red. Volcanic, or sea vent?
Also I notice the coast lines are more green and blue and the open oceans, which seems to contradict tty who says “pH over 8.25 is not unusual in areas with high biologic activity where algae “eat” the CO2. Over coral reefs pH can touch 9.0 in late afternoon.” The graph seems shows the opposite. The PH is lower along the coast lines.

Accuracy of sea water measurements with glass pH electrodes:http://cdiac.ornl.gov/ftp/cdiac74/sop06.pdf
SOP 6: Determination of the pH of seawater using a glass/reference electrode cell.
9.2.2 Precision (with care) 0.003 pH units (1 SD).
9.2.3 Bias <0.004 pH units.
REPRODUCIBILITY OF pH MEASUREMENTS IN SEAWATER’ (www.aslo.org/lo/toc/vol_11/issue_3/0417.pdf)
"The data obtained by current oceanographic procedures, in which dilute buffers are used, will be shown to be comparable within 0.006 pH units".
So the methods are fine if applied correctly…
HTH

Is there a source where I can download an unadjusted global temperature dataset? Actual temperatures, not averages or anomalies, in an easy to use format. Preferably without any attempt to correct for sample density, time of day, or anything. land and ocean, something like:
location, date, time, temp.
I’d like to try and replicate what I did with ocean pH data, instead using temp data. I’m encouraged that the gridded result was virtually identical to simply treating the raw data as a random sample. thanks in advance.

The gridded result:Berényi Péter December 31, 2014 at 8:58 am
A preliminary look at the data shows beyond doubt, that ocean pH is decreasing indeed, at a rate of -0.002±0.038/decade. In other words, it is absolutely stable.
delivers virtually the exact same answer as simply treating the data as a random sample, without any gridding, averaging, anomalies, adjustments, etc.ferdberple December 31, 2014 at 8:29 am

These scatter diagrams are worrisome. The variance changes substantially in time, suggesting a sampling problem. Why does the recent trend here disagree with the Feely et al results and the Japan results shown above? If the data set was broken up into separate regions (say eastern N. Pacific, western N. Pacific, Atlantic, Indian Ocean, south pacific, south Atlantic), what would the trends and variability look like?
…cliff mass, UW

The variance changes substantially in time
============
Not correct. For almost every year the variance well under 0.1 pH, which suggests the samples in the scatter diagram are consistent. Keep in mind these samples were taken from all the oceans over many years, while it would appear that Feely et al and the Japan samples were not.http://oi59.tinypic.com/95u0ip.jpg

Ferd
I may not have been clear. Look at the variability of the ph measurements in the figure (ph versus time for all observations). It various hugely—some periods it ranges from 6 to 10, while in other periods (like the recent one) one quarter of that. Isn’t that a problem?..cliff

Cliff
The variance is a function of the number of measurements. The graph shows both the number of measurements and the standard deviation of the measurements by year–since the number of measurements sharply declined around 1990 the variance increased.https://dl.dropboxusercontent.com/u/75831381/pH%20variance.jpg

some periods it ranges from 6 to 10, while in other periods (like the recent one) one quarter of that
===============
You would expect the visual spread to increase as the number of samples increases. For example, 1000 people will be expected to have a wider range of opinions than would 10 people, with the variance unchanged. In this case mostly < 0.1 pH.
The spread is not an issue. pH changes by season, time of day and location. Just like surface temperature. One could go through a complicated statistical process, and try and adjust for these variables, such as done for temperature. For example, by calculating averages, anomalies and grid the results by location. This will make the data all appear to be tightly grouped and very accurate.
But in reality, with enough random samples, the brute force approach should give approximately the same result as the more complicated and detailed approach. As was confirmed in the gridded analysis see: Berényi Péter December 31, 2014 at 8:58 am for confirmation.
There is some small trend in the variance, maybe modern scientists are not quite as careful as in the past.http://oi57.tinypic.com/211mji1.jpg

The above trend is not a sample of the real world, as the year by year sampling differs in track, ocean and direction (east-west, north-south) and season.
Compare the cruises for each year:http://www.abeqas.com/ph-1990s/ andhttp://www.abeqas.com/ph-2000s/
Berényi Péter has looked at 5×5 grid boxes over the past decades and found:
If only grid boxes with at least 20 years of data are considered (204 items), ocean pH trend is -0.002±0.031/decade, therefore the null result is reasonably robust.
I have given a try to grid box / month combinations with at least 30 years of data (81 items). The result is +0.003±0.026/decade, therefore the null result is incontrovertible.
The trend measured by Sabine and others over the past 30 years was 0.013±0.007/decade, which is within the error margin of all (GE?) pH measurements, even as the “null result” from Berényi Péter therefore is broken (the pH change caused by CO2 is very small).
That means that the glass electrode pH measurements simply can’t measure the faint change in pH over the past decades (which is what Dr. Sabine said), let it be the even much smaller change per decade over the period 1850-1984.
What I wonder is when the glass electrode measurements were abandoned (for the Hawaii station that was 1992) and replaced by colorimetric or calculated values, also in the ship’s surveys.

If I restrict the data to depth =0, I get N = 197762 with a slope of 0.0009 (SE=0.0003), z = 31 which, although significant, is close enough to your conclusion of “no trend” for me not to disagree.
However, to compare to Feely’s choice of the 1988-2007 time period, the result is N=27325, slope of -0.01025 (SE 0.0003), t-value = -34 (highly significant). And this slope is again much steeper than that provided by Feely.

Feely’s choice of the 1988-2007 time period
=========
when I restrict the data to 1998-2007 I get a very slight negative trend for depth = 0. I would not consider this significant because the brute force approach is inherently crude. The full set of years showed a slight positive trend which I also did not consider significant.http://oi59.tinypic.com/o8wk9g.jpg
I didn’t include data for depth > 0 because of the improvements in underwater technology. While surface transport has been largely unrestricted for the past 100+ years, the same cannot be said for underwater work. I would have needed to add a depth adjustment, which I didn’t want to do, because I might then end up measuring the adjustment, not the true trend.

Fitting a time series using ordinary least squares (OLS) linear regression is frowned upon by many statisticians, since OLS is known to be biased toward low slopes and high intercepts, and the slope can be strongly affected by outliers. However, one can at least compare the results from this database with those of Feely. It is at once evident that both this database (censored to restrict pH to values between 7 and 9) and the different one used by Feely show a decline in pH between 1988 and 2007. Here are the results:
N = 585083
slope = -0.0113 (SE=0.000047)
z = -242
This slope is much STEEPER than that shown by Feely (about -0.002).
For the full set, the values were
N = 2,437 X 10^3
slope = -0.00178 (SE=0.000010)
z=-185
It seems to me that these data should NOT (as is apparently being advocated by Ferdinand Engelbeen) be ignored. But like the temperature data, the pH data need to be carefully studied and efforts made to apply QA/QC considerations.

If climate scientist are advocating that we ignore this data, because it is not the most accurate available (while ignoring that it is provides the best coverage for time and location) then by the very same argument we should ignore the thermometer data from weather stations and only use the much more accurate satellite data.
but instead what we are hearing is that we should only use the data-sets that co-incidentally show the results that match theory. because the other data-sets must be inaccurate, because they don’t match theory.
that isn’t how science works. you need to include all the data-sets. the uncertainty in your result is determined by the spread between the data-sets.

It appears that there was a jump in pH during the period when many more observations were available (roughly 1970-1990). Thus, I wonder whether the drop off in pH might be in part a sampling issue. Did the geographical areas of sampling change over time? Was there a change in the geographical distribution as N dropped substantially? And why is mean pH dropping in the 8:50 AM comment but not in the scatter diagrams?

And why is mean pH dropping in the 8:50 AM comment but not in the scatter diagrams?
=============
the scatter diagrams are depth = 0 only. The pH drop in the 8:50 comment appears to result from an increase in samples with depth > 0, starting in 1980 and accelerating in 1990.

Well, actually at 10:19 AM I kind of disproved myself, because I regressed the 1988-2007 data on surface measurements only (N=27,000) and got almost exactly the same slope (-0.010 vs. -0.011) as had been found at 10:06 using all the data (N=585,000).

Fascinating discussion. For my part, it is interesting to look at the apparent oscillatory behavior within the limited time span. Once one approaches this from a viewpoint of possible oscillations, then assertions regarding linear trends must share the stage with that. Moreover, by applying a variation of the 10 year moving average, I think I had begun to account for concerns regarding localized and moving data stations, given ocean circulation rates.
In addition, given the reality of ocean circulation and mixing, it is interesting to look at the 1910-1920 data http://www.abeqas.com/global-ocean-ph-measured-1910-1920/
and see how it roughly captures the profiles of later decades (see same site, other decades featured), even though the sampling locations in 1910 – 1920 set were severely limited in geographic extent compared to later decades.
For what it is worth, the relation of the data time series construction for a 10 year trailing average (yta) to the 10 yta for the Pacific Decadal Oscillation (PDO) is of great interest to me.http://www.abeqas.com/global-ocean-ph-pdo/
In fact it was an inspiration for much of the work I have done this year regarding successful use of the PDO as a hydrologic forecasting tool in the US Southwest. Had I not observed this interesting similarity between the PDO and ocean pH curves (10 yta version), I might not have decided to attempt to produce a hydrologic forecast for my subject area. Now I have a successful forecast under my belt (is not that a possible signature of real scientific progress?) and I now collaborate with Dr. Petr Chylek of LANL on further integration of ocean oscillation based (and other drivers) hydrologic forecasting.
I note finally, that the omission of this data was the primary news feature. I don’t understand how anyone can conclude that the omission actions are remotely defendable. As many have stated, this is wrong, regardless of any opinion one develops concerning this data after the fact.

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